Nghiên cứu quan hệ giữa tính chất và cấu trúc dãy Anpha, Beta-Xeton không no chứa dị vòng Thiophen bằng phương pháp tính gần đúng lượng tử

Bạn đang xem bản rút gọn của tài liệu. Xem và tải ngay bản đầy đủ của tài liệu tại đây (28.5 MB, 98 trang )

(1)<div class='page_container' data-page=1>

BO GIAO DUG VA DAO TAO

DAI HOC QUOC GIA H A N O I

TRirdNG DAI HOC KHOA HOC lUNHIEN

Le Thai Binh

NGHIEN COU QUAN HE

GICA TINH

CHAT VA CAU TRUC DAY

a,p - XETON KHONG NO CHLfA Dl VONG THIOPHEN BANG

PHl/ONG

PHAP

TINH GAN

O O N G

Ll/ONG TLf

LUAN AN THAC SI KHOA HOC HOA HOC

Chuyen nganh : Hoa Ly

Ma so: 1-04-04

Ngudi huong dan khoa hoc :

PGS.TS Lam Ngoc Thi6m

^ ' • " • ' j i . A

Ha noi 2 0 0 0

jlA hA iiO' I

</div>
(2)<div class='page_container' data-page=2>

LOl CAM ON

Vdi Idng hiet ari sdu sac toi xin chdn didnh cam 
an su huang dan tan tinh, day trdch nhieni cua thdy 
gido huang dan PGS. TS Lam Nggc Thiem.

Toi Cling xin chdn thdnh cam an cdc thdy c6 
gido trong Khoa Hod, to ho mdn Hod ly cung todn 
the ban be gia dinh da dong vien khuyen khich, tao 
dieu kien vd giup da toi hoan thdnh ban hum an nay.

Hd ngi thdng 6 nam 2000

</div>
(3)<div class='page_container' data-page=3>

MUG LUC

Trang

Md dau 1
Chuong 1 : TONG QUAN 3

1.1 Sir phat trian va ly thuyet cac phuomg phap tinh gan dung trong hoa 3
hoc lugng tir

1.2 Cac quan diam nham giai gan diing phuong tnnh Schroedinger 6
1.2.1 Phuong trinh Schroedinger va phep gan diing Bom - Oppenheimer 6

1.2.2 Ly thuyet trudng tir hop Hartree Fock ( Harlree Fock SCF ) 8

1.2.3 Phuong irinh Roolhaan 11
1.3 Cac phuong phap giai gan dung 13

1.3.1 Phirong phap AB initio hay phuong phap linh khong kinh nghiem 14

1.3.2 Cac phirong phap ban kinh nghiem 14
1.3.2.1 Phuong phap gan diing Huckel ( HMO) 15

1.3.2.2 Phirong phapCNDO ( Complete Neglect of Differential Overlap ) 16

1.3.2.3 Phuong phap INDO ( Intermedate Neglect of Differential Overlap ) 17
1.3.2.4 Phuong phap MINDO ( Modified Intermediate Neglect of Diatomic 18

Overlap )

1.3.2.5 Phirong phap MNDO (Modified Neglect of Diatomic Overlap ) 19

1.3.2.6 Phuomg phap AMI ( Austin's Model 1) 20
1.3.2.7 Phirong phap PM3 ( Parametric Model 3 ) 20
1.3.2.8 Phirong phap ZINDO/S ( Zemer\s INDO ) 20

1.4 Doi tirgng nghian ciru ciia da lai 23
1.4.1 Dae diam \e cau iriic ciia hop chat khao sat X- C i . R p S 24

1.4.1.1 Nhan phenyl va vi iri the para 24

1.4.1.2 Nhan ihiophen 26
1.4.1.3 Nhom carbonyl va sir dich chuyen electron trong mach 27

Chircmg 2 : PHAN THUC NGHIEM VA BIEN LUAN KET QUA 30

2.1 Phrin mem \'a cac biroc lien hanh nghien ciru. 30

</div>
(4)<div class='page_container' data-page=4>

Trans

2.4 Phat trian mach 35
2.5 Anh huong cua nhom the para - phen\'l ihuoc phan tir A4X \a B2X 45

2.5.1 Anh huong cua nhom the Ian nang lugng loan phan. nang luong lien 47
ket, nhiet hinh thanh

2.5.2 Anh huong cua nhom the len gia tri momen Iiroiig cue 49
2.5.3 Anh hucmg cua nhom the lan dien tich cua nguyan tir Oxy ^^

2.5.4 Anh huong ciia nhom the Ian dien ifch cua nguyan tir S va di vong
ihiophen

2.5.5 Anh huong cua nhom the den dao dong ciia phan tir 58

Chuong 3 : KET LUAN CHUNG 61

Tai lieu iham khao 63

</div>
(5)<div class='page_container' data-page=5>

MOOAU

Ngay nay phuong phap hoa hoc luong lir da dugc ap dung vao hau het cac
17nh vuc cua hoa hoc va da dal dugc nhung thanh lu dang ka. Sau gan 30 nam iha
nghiem vdi bao bude thang tram, cuoi cung thuc lian da xac nhan phirong phap
hoa hoc lugng lu da Iro thanh phuong phap khong the thieu dugc trong nghien ciru
hoa hoc hien dai. PhSn ihudng Nobel nam 1998 ve hoa hoc tang cho giao su J.
Pople - cha de cua cac phuong phap tinh gan diing hoa lugng tu - la mot minh
chung cho nhung nhan xet nay.

Dua vao ket qua tinh cua cac phuong phap gan diing ngudi la da xac dinh
kha chfnh xac cac tinh chat lugng tu nhu mat do electron, dien ifch hieu dung trcn
tung nguyen tu, bac lian ket, chi so hoa tri tu do.. . Cac Ifnh chat vT mo ciia phan tu
nhu cau triic, the ion hoa , nhiet hinh thanh, momen luong cue, tan so quang pho ..
. Cung bang phuong phap nay cac dai lugng nhu do dai lien ket gdc van, gdc nhi

dien.. . da dugc xac dinh luong ddi chinh xac so vdi cac gia tri do dugc bang thuc
nghiem.

Co the ndi phuong phap hoa hoc lugng lir khong phai la mo hinh trang trf
hoac nhung phae thao via'n vong tren giay nhu ngudi ta ludng trudc day ma no da
thuc sir tro thanh cdng cu huu hieu khong tha ihay the trong nghian cuu hoa hoc.

Ap dung cac phirong phap lugng tu trong ban luan van nay chung toi can
giai quyet cac van de chinh sau day :

</div>
(6)<div class='page_container' data-page=6>

tfch cd do chon Igc. do nhay cao va la nhung san pham irung gian cho nhieu qua
trinh tdng hgp huu co quan trong.

2. Tran co so nhung so lieu ihu dugc chiing toi se xem xet mdi luong quan
giua cau tnic va tinh chat cua phan tir nhu qui luat phan bd electron trong phan tu.
anh huong cua cac nhdm the den qui luat nay, cau dang uu lian va kha nang phan
ung.

</div>
(7)<div class='page_container' data-page=7>

CHirONG 1 -TONG QUAN

1.1- Sir phat trien ve ly thuyet cac phuong phap tinh gan diing trong hoa hoc 
lugng tu

Hoa hoc lugng tu cd the coi la sir ap dung co hoc luong tu vao hoa hoc
nham giai quya't va mat ly thuyet cau triic. quan he giua tinh chat hoa hoc \'a cau
triic cua cac nguyan tu va phan tu. Tran quan diem ciia hoa hoc lugng tu. mot ddi
lugng khao sat ( nguyan tu, phan tu, ion, gdc tu do v.v.. ) dugc xac lap neu nhu xac
dinh dugc ham sdng \\J va nang lugng E cua he cung nhu cac dai lugng lugng tu, 
cac thong so cau tnic va cac tinh chat hoa ly khae.

Theo hoa hoc lugng tu, sir bien ddi trang thai cua he vat ly vi mo dugc biau
dian bang phirong trinh sdng Schroedinger 6 trang thai dung | 9 | :

Hi/^{q)=E{q)

E - nang lugng
v[/(q) - Ham sdng
q la yen to toa do

// - loan tu Halminlon ciia he ,

II = T -¥]' { V - the nang cua he, T - dong nang cua he )

</div>
(8)<div class='page_container' data-page=8>

Tu phuong trinh Iran loan tu H c6 dang

H = t e + t n + Uee + Uen + Unn
Trong dd :

f e - dong nang cua electron

j ^ - dong nang cua hat nhan

U^^- the nang luong lac giua cac electron \di nhau

(] ^n - the nang tuong tac giua cac hat nhan va cac electron

{j „^ - the nang tuong tac giua cac hat nhan vdi nhau

Mot each Idng quat, gia sir mot phan tu cd N hat nhan va n electron

Do khoi lugng nguyan tu tap trung o hat nhan nan, mot each gan diing, coi
hat nhan cd dinh. Vay H trong phirong trinh Schrodinger chi bao gdm ba thanh
phan ;

A A A A

H = Te + Uen + Uee

Dfiu lien de de giai phuong trinh sdng. Born - Oppenheimer chi quan lam
den dong nang cua electron t e va the nang tuong lac electron - hat nhan fj,,,, liic
nay loan tu Halminton cd dang :

H* = t e + Uen
Day la gan diing bac khong.

</div>
(9)<div class='page_container' data-page=9>

Dd'i vdi ha phan tu, so vdi quan diam cua Hartree Fock, he con cd tham cac
luong tac giua cac hat nhan khae nhau vdi electron . Do dd la khong tha ap dung
phuong phap Hartree Fock de giai quyet dugc van da nay. Roolhaan da da nghi
mot phuong phap mang tan dng. Ham sdng phan tu MO dugc mo la nhu Id hgp
luyen tinh cua cac ham sdng co so MO-LCAO ( cac ham sdng co so dugc goi la
tap ham co so ) . Bang phuong phap irudng tu hgp - SCF . Roolhaan tim dugc he
nghiem cac ham sdng md la he nhiau hat trong phan tu, ham sdng nay cd dang la
Id hgp luyen tfnh cac ham co so vdi cac he so thich hgp. Cho den nay phuong trinh
do Roolhaan dua ra la co so cho cac phuong phap tinh gan diing sau nay.

Den nay cd ba huong phuong phap da giai gan diing phuong trinh
Roolhaan.

DAu ticn la phirong phap ihuan tuy loan hoc AB-initio | 12|, trong phucrng
phap nay, ngudi la sir dung cac phuong phap gan diing loan hoc nham don gian hoa

qua trinh giai. Phuong phap nay nhin chung ddi hoi linh loan kha phi'rc tap nc'u so
vdi hai phuong phap sau, nhung mat khae cd tha ap dung cho hau het cac dang
phan tir.

Phuong phap ihu hai dua vao cac quan diam ve can hinh hoa hoc de don
gian hoa qua trinh giai bang each giam so ham co so xay dung nan orbital phan tu
114].

</div>
(10)<div class='page_container' data-page=10>

1.2- Cac quan diem nh^m giai gan diing phuong trinh Schroedinger •

Nhu da biet, phuong trinh Schroedinger trong cac he nhieu hat ndi chung la
ra'l phiic lap, khong tha giai dugc chinh xac. Do dd cac nha khoa hoc ludn lim cac
phep gan diing nham don gian phuong trinh, bien chiing cd tha giai dugc. Theo
mirc do phiic tap cac phep dd la : phep gan diing Born - Oppenheimer, Hatree Fock
va Roothaan.

1.2.1 - Phuong trinh Schroedinger va phep gan diing Born - Oppenheimer

Co hoc lugng tu da giai thich dugc tfnh chat ludng tinh sdng - hat cua cac
hat vi md, phuong trinh Schroedinger la phirong trinh sdng md ta he cac hat vi md.
Phuong trinh cd dang l6ng quat;

H\\f{q)=Ex\}{q) ( 1 . 0 1 )

Trong dd \|/ la ham sdng md ta he chi phu thude vao toa do cac hat trong he ( c/) 
ggi la ham sdng d trang thai dung, tich ciia i(/ va lien hctp phirc ciia nd \|/* cho la
bici xac suai bat gap hat, E la nang lugng , H la loan lii Hamilton bao gdm hai
thanh phan dong nang va the nang cua he :

-H = t + V (1.02)

Trong dd

T : Toan tu dong nang cd dang T = h' V'/ 87i'm (1. 03)
Vdi h : hang sd Planck, V^ : toan tu Laplace, m : khoi lugng hat.
V ; Toan lii the nang cd dang V = -q,qV r

</div>
(11)<div class='page_container' data-page=11>

Phuong trinh (1.01) edn cd tan goi la phuong trinh Schroedinger khong phu
thuoe thdi gian. Chii y rang phuong trinh nay khdng md ta diing cac he trong do 
toe do chuyan dong ciia cac hat gan bang toe do anh sang (. \i du nhu he cac 
electron Idi chuyan dong gan cac hat nhan Ion ).

Doi vdi he bao gdm cac hat nhan va electron loan tu H trong phuong trinh
(1.01) cd dang ;

H = t e + t n + Uee + Uen + Unn (1.04)
H(l,2..N;l,2..n) thi toan tu ^ c d dang:

^ = -^t^y'^-V^t K-TI.^'Z,r:^.l^e^Z,Z,r-l.j:e^r-; (1.05)

8;r' ^ " " STT-m A

6day :

M,, Z, la khoi lugng va dien tich cua hat nhan i
m la khoi lugng cua electron

e la gia tri dien tfch ciia electron

r ,, la khoang each giua hai hat i va j bai ky (i,j cd tha la A,B,p, q v.v..)
A,B, p, q la cac chi so da phan biet cac hat nhan va cac electron riang biet.

</div>
(12)<div class='page_container' data-page=12>

!H = - - 4 M ; v=-xi;.^z,.;>x.v-/ (1.06)

OTT m J A p p<q

Trong ly thuyet orbital phan tu chiing ta thudng chi quan tam den cac ham
sdng cua cac electron , do dd thudng chi sir dung toan tu ^{^ hay vi sir dung loan tu 
H. Phuong trinh Schroedinger sau khi da dugc Born - Oppenheimer sua ddi cd
dang :

Jt \\f(q) = E\\f(q) (1.07)

Do chenh nang lugng £ thu dugc do giai phuong trinh (1.07) va E do giai phuong
trinh (1.01) la phan the nang tuong tac day giiJa cac hat nhan :

E = ' £ + ^e-Z^,Z^r AB 1 
A<fi

Nhu vay Born - Oppneheimer da don gian lam cho toan tir H trong phirong 
trinh Schroedinger ban dfiu chi con ha thanh phfin lien quan den dong nang ciia
electron , the nang tuong tac giiia electron va hat nhan dugc coi la dung yan, va
the nang tuong lac giua cac electron vdi nhau. Vdi phep gAn diing nay , phucrng
Irinh Schroedinger da don gian di nhung van edn phiic tap khi giai nhat la thanh
phan cudi ciing trong phuong trinh (1.06) - the nang luong lac giua cac electron
vdi nhau. Hartree Fock da tiep luc giai quyet van de nay.

1.2.2 Ly ihuvet irudng tu hop Harlree Fock. ( Hartree Fock SCF )

Trong ba thanh phan ciia phirong trinh ( 1.06) Hartree phan biet : hai thanh
phan dau chi lien quan den mot electron khi dd phuong trinh (1.06) cd dang :

// = / / ' X Z e'r-; (1.08)

n

Harlree coi ham sdng ciia he \|/ = ]~[ (// ' (1.09)

</div>
(13)<div class='page_container' data-page=13>

Dd'i vdi he nguyan tu bao gdm mot hat nhan \ a n electron . H = Z^H

Di dua toan tu cho boi phuong trinh (1.08) chi lian quan den toa do cua

mot electron Hartree da lay trung binh :

r -> \ 
e

II'%; = I I 7 =11^.

p-di t J

(LIO)

V 'V y

TB

Trong dd J,j dugc goi la tfch phan Culdng

j^^= ^^¥^eV]dT,dr, ( 1 1 1 )

Tdm lai, theo Hartree loan tu Hamilton ciia he nguyan tu nhieu electron cd

dang :

Dd'i vdi he nguyan tir, nghTa la sir phan bo electron quanh hat nhan cd dang
hinh can, the nang cua electron chi phu thude vao khoang each cua nd vdi hat
nhan , moment gdc la hang sd khi dd la cd the' giai dugc phirong trinh (1.10) neu
cd mot ham i|/ cho Irirdc. Dd la phep gan diing do Harlree Fock de nghi.

</div>
(14)<div class='page_container' data-page=14>

Tuy nhian ham sdng \\f tim dugc tiJ phuong trinh (1.09 ) la ham ddi xihig .

ngugc vdi nguyan ly Pauli. Fock da cai tien til ham sdng Harlree liic na\' ham v|/
cd dang:

\\) = I//. <j (1.13)

Trong dd:

a la ham spin

^ l a ham sdng trong phuong trinh cua Harlree.

Vdi ham sdng orbital spin nayham sdng ciia he dugc Fock td hgp dudi
dang:

i|/=(N!)-'^^|^,(T/y)| (1.14)
C) day \y/,a^(jy la dinh thuc Slater, N la Idng sd electron trong he. Viec chuyen vj

hai electron lUcyng duong vdi viec hoan ddi vi trf hai col ciia dinh thuc dan den ddi
da'u .Vdi hieu chinh ciia Fock, ham sdng tim dugc la ham phan ddi xirng phu hgp
vdi nguyen ly Pauli .

Fock edn cd mot ddng gdp quan trong trong viec trung binh hoa the tuong
tac giiia cac electron vdi nhau [29]. Ham sdng Hartree dugc td hgp dudi dang

N

tfch Harlree, nghTa la ^'1 = YW^^' • ^^^ ^^ thuyet vi xac suat cd nghTa la Hartree

coi die electron chuyen dong doc lap ddi vdi chuyen dong cua cac electron khae.
Khi tfnh loan the tuong tac trung binh electron - electron . Hartree chi chii y den
tfch phan Culdng J,,. Dieu nay cd nghTa Hartree chi chii y den tuong tac tTnh dien
irirc liep giua cac electron /. / ma khdng quan lam den anh huong cua Irudng do
cac electron edn lai . Trong phirong phap Fock, nang lugng ciia he theo cai lien
ciia Fock la :

^ = Z^"' + ZZ-^""^-ZX^'.^> (1-15)

m m<.n m

</div>
(15)<div class='page_container' data-page=15>

E^ - nang lugng bao gom ddng nang electron va the nang do tuong tac hiit

giiia hat nhan va cac electron .

Jn,n la tfch phan Culdng dac trung cho tuong tac day giua hai electron chiem
hai orbital m va n :

Krnn 1^ tfch phan trao ddi tfnh vdi Irudng hgp hai electron i va j

•>

K^„ = J K ( ' k ( ' ) f V^.OkO>/r,^r^ (1.17)

Nhu vay Fock da dua vao trong the trung binh thanh phan K^in dac trung
cho tuong tac trao ddi giiia cac electron . Phuong phap Hartree Fock dugc coi la
phuong phap kha hoan chinh de giai cac bai loan nguyen tii [30j.

1.2.3 Phucrng irinh Roolhaan

Nhu da biet phuong phap Hartree Fock khdng the ap dung ddi vdi he nghien
cuu la Ccic phan tu. De giai quyet van da nay, Roolhaan da dua ra phirong phap cua
minh. Phirong phap Roolhaan sii dung phuong phap bien phan , chon cac ham
Ihich hgp la td hgp tuyen tfnh ciia cac ham (t),, cac ham (j), lap thanh bo ham co sd
da bieu dian cac orbital va diau chinh cac thdng so ciia nd de chuyan chiing vi 
dang gan vdi cac orbital Hartree Fock. Dd la quan diem cua phuong phap
Roolhaan.

Thdng ihudiig ngudi ta sir dung ba bo ham co sd nhu sau :

Cac bo ham co sd toi ihia'u ; bao gdm cac AO , cac orbital ciia Idp vd hoa
Iri cua mdi nguyan lii trong phan tu.

Cac bd ham ca sd mo rgng : nhu cac bo ham co so toi thieu cd tfnh them 
vao cac AO nam ngoai Idp hoa tri ciia mdi nguyan lii.

Bo ham co sd hoa tri : Chi bao gdm cac orbital ciia Idp hoa iri ciia mdi
ngu\'en tu.

</div>
(16)<div class='page_container' data-page=16>

Con cac orbital cua Hartree Fock la nghiem cua phuong trinh :

Viec di6u chinh cac he so 3,^, de ham song v|/ co dang gan giong \6'\ 
orbital Hartree Fock. dong nghTa voi gia tri E^ dat circ tieu, trong do E^, :

E.=

k'A

(1.20)

Ap dung cac quy tac bia'n phan la thu dugc he cac phuong trinh Roothaan
dudi dang :

I ^ / J ^ , - V J = 0 v6rii:l,2...M (1.21)

trong dd M la sd bd ham co sd , E^^ la nghiem ciia phuong trinh :

F^_,-ES^^ =0 (1.22)

d day F,j la thanh phan cua ma tran Fock va dugc xac dinh : F^^ = {(p^Ttp^d^ 
Sjj - la tfch phan xen phii .

Di giai ham sdng nay, Roothaan sii dung phuong phap tu hgp cua Hartree

Fock

Tii bo ham co sof (j)/, Roolhaan giai lap mot ham sdng MO y/^ tuong ling vdi cap 
cac he sd a^ :

^ > Z O ' (1.23)

Sir dung ham \|/" de' xac dinh toan tir Hartree Fock tirong ijng H ' r6i sir dung giai

</div>
(17)<div class='page_container' data-page=17>

Nang luong cua mot electron lai MO \i thu dugc cd dang tuong tu Hartree 
Fock

^. = ^. ^ 1(2^.. - ^.J

(1.24

Trong do e^ dai dien cho ddng nang ciia mot electron tai MO |.i \'a the tuong tac 
hiit gay ra bdi cac hat nhan ( thdng ihudng ggi la nang lugng tuong tac Idi ),

y]{2J^ - K^ ) la gia tri trung binh the nang luong tac cua electron lai MO |i

vdi cac electron khae trong phan tii. Trong qua trinh tfnh loan theo phuong phap
Irudng tu hgp SCF, y/^ la MO dau tian ma Roothaan giai lap da tfnh loan

J,^^ dac trung cho tuong tac day trung binh ciia electron dang chiem MO i//^^ va 
mot electron dang chiem MO ^//," , theo Roothaan nd cd dang cu the

•^... = i\I.^'jM

JI^JM)

' i : L i(

!",;>. (2)

Z^',/>.(2)

dr^dz-, (1.25)

K li, ifeh phan trao ddi cd dang :

^.^ = W

Z «.>,(!),

Z^^'V.O)

''r.

K<p,i'~)

Z^'./>X2)

Jr.dr, 26)

Phirong trinh Roothaan la co so cua cac phuong phap tfnh sau nay bao gdm
cac phuong phap tfnh loan gan diing loan hoc AB - initio va cac phirong phap ban
kinh nghiem (semi- empirical). Hau het cac phuong phap dau tap trung vao viec
giai quyet van de the nang tuong tac giua cac electron vdi nhau . Va mat toan hoc

dd la qua trinh giai gan diing cac phuong trinh chiia cac tfch phan Culdng va cac
tfch phan xen phu giua cac electron .

1.3 - Cac phirong phap giai gan dung :

</div>
(18)<div class='page_container' data-page=18>

giam sd ham co so Mulliken va cac phuong phap ban kinh nghiem sir dung cac
tham so thuc nghiem: CNDO. NDDO. INDO. AMI PM3. MINDO. ZINDO.. .

1.3T - Phuong phap AB -initio hay phuong phap tfnh khdng kinh nghiem :

Phuong phap AB initio khae vdi cac phuong phap ban kinh nghiem o cho la
trong qua trinh tfnh loan khdng sir dung cac tham sd tii thuc nghiem [221. Thay vao
dd qua trinh tfnh loan chi sir dung cac qui luat cua co hgc lugng tu va mot vai hang

s6 vat ly [ 19 ] bao gom :

- Toe do anh sang trong chan khdng.

- Dien tfch va khoi lugng ciia electron va hat nhan
- Hang sd Planck...

Phirong phap AB-initio dua vao cac phep gan diing loan hgc o mire nghiem
ngal 120] . Sir khae nhau giua phuong phap ban kinh nghiem va phucrug phap
initio la sir phiic tap trong tfnh loan va do chfnh xac ciia ket qua. Phirong phap
AB-initio cd mot Idi giai kha chfnh xac cho hfiu het cac he phan tii. Cung cd the ndi
phirctng phap AB-initio la sir tfnh ti^r dau cho tat ca cac tfch phan bang phep giai
tfch 121]. Mac dii phirong phap AB-initio cd do tin cay va chfnh xac cao nhung nd
cung cd Ccic han che nhu can bo nhd Ion, idc do tfnh cao, thdi gian linh loan lau
hon nhieu lan so vdi phirong phap ban kinh nghiem.

1.3.2 - Ccic phUQ-ne phap ban kinh nghiem :

</div>
(19)<div class='page_container' data-page=19>

thuan ly thuyet. Nhd sir loai bo hang loat cac tfch phan, cac phuoiig phap gan dung
ban kinh nghiem lan lugt ra ddi. Ta xet mot sd cac phuong phclp sau :

1.32.1 Phirang phap gan diing Huckel ( HMO)

Ngay tii nam 1931, can cii vao cac tfnh chat hoa hgc dac trung cho he
phan tu huu co lian hgp n , Huckel da da xudng phuong phap HMO ( Huckel's 
Molecular Orbital). Phuong phap nay ra ddi da gdp phan dinh lugng hoa cac dai
lugng nhu mat do electron q,, bac lien ket p^, , chi sd hoa tri tu do F, .. . di xet 
doan CO che cung nhu cau dang ciia mot sd hgp chai huu co he lian hgp.

MO - Huckel la phuong phap td hgp luyen tfnh cac AO nhung chi ap dung
dd'i vdi Ccic electron n. Bang vice ap dung phuong phap bien phan, xac dinh gia tri 
ruing lugng va ham sdng ciia he electron TI qui vi giai he cac phuong trinh :

\H„-S„E\ = 0 (1.27)

trong dd, vc irai dugc ggi la dinh Ihiic the ky.

H va S la cac ifch phan. Huckel da de xuat each xap xi trung binh nhu sau :
Neu i=j thi H,j = a ggi la tfch phan Coulomb

Neu i;^j thi H,, = [3 ggi la tfch phan trao ddi
Cac Irudng hgp edn lai : H,j = 0

Tuctug tu nhu vay, ddi vdi tfch phan xen phii S ta cd :

Na'ui=jlhi S,j=l (1.28)

Neu i^j thi S = 0.

Trong cac Irudng hgp lian hgp va siau lian hgp cd chiia cac di to cac gia tri
ciia a \ a [i hi thay ddi vdi cac gia tri tfnh ti^r cac he khdng chira di to mot he sd (
thdng thudng cac he sd dugc xac dinh bang thuc nghiem ddi vdi tung he cu the ):

</div>
(20)<div class='page_container' data-page=20>

Tuy nhien phuong phap HMO da bo qua tuong tcac day ciia cac electron a
nan pham vi ung dung chua dugc mo rgng. Da khc^c phuc dieu na\ Hoffman da
phat trien HMO thanh phuong phap Huckel mo rgng ( Extended HMO ). Trong
phuong phap nay ngudi ta da tien hanh tfnh cac tfch phan xen phii S,, thay cho viec
gan cho nd nhung gia tri tuy y. Phuong phap MO- Hucken mo rgng diing da tfnh
loan nang lugng, khdng diing de td'i uu hoa hinh hgc hay tfnh loan cac thdng sd
nhiet ddng phan tii. Ket qua cua phuong phap nay cho ta mot sir md ta cac orbital
phan tu d muc dinh tfnh va ban dinh lugng, cac tfnh chat nhu dien tfch dinh cU va
sir phan bd spin. Vdi phuong phap nay ket qua tfnh da kha di ho*n nhung van dung
d muc gan diing ihd.

1.3.2.2 Phuangphdp CNDO { Complete Neglect of Differential Overlap )

Tan cua phuong phap cd nghTa la bo qua hoan toan cac vi phan phu ciia cac
electron thude cac nguyan tu khae nhau. Day la phuong phap ban kinh nghiem
don gian nhat tfnh loan theo phirong phap Irudng tu hgp. Nd dugc diing da tfnh
loan die tfnh chai ciia electron d trang thai co ban, ddi vdi ca he vd md v;i he vd
ddng, toi uu hoa hinh hgc va Idng nang lugng. Trong phuong phap CNDO, chi xet
den cac electron hoa tri , Idp vd tro dugc coi la mot phan cua Idp Idi, va gdp tuong
Uic day cua lop nay vao tuong tac cua hat nhan vdi electron .

Nhu da biai trong phuong phap Irudng tu hgp qua mdi qua trinh tfnh loan
ngudi la deu sir dung gia tri nang lugng nhu la mot tiau chi de danh gia sir hoi tu
qua dd tim dugc ham sdng luong ung vdi mot bd ham co sd cu the.Theo phuong

phap bicii phan va bang each bien ddi loan hgc ta thu dugc nang lugng electron
Idng cdng cd dang :

* - • t - . *_

l^ = Y.I\JI,.^,^\'2j^jw\Aa,-\;2 MO Aa] (1.29)

uu Ul>AG

Trong dd :

Ppv la cac yen Id ma Iran mat do

</div>
(21)<div class='page_container' data-page=21>

Phuong phap CNDO don gian hoa phuong trinh Roolhaan bang each xu ly

pv\^a)

n^y-Quan diam gan diing cua phuong phap CNDO cd tha coi la tdng hgp ciia 5
phep xap xi sau :

1. Thay the ma tran xen phu bang ma tran don vi trong phirong trinh
Roothaan, bo qua cac tfch phan xen phu 5^^, trong qud trinh chuan hoa cdc orbital
phan tu.

2. Bo qua tfch phan xen phu trong tat cac cac tfch phcan cd hai electron

{lJv\?La) = {pv\Xa)5^^^5^_^ trong dd 6 la cac delta Kronecker

3.Trung binh hoa cac tfch phan Culdng ddi vdi mdi cap electron

{po\Xa) = ?i.^f, {(p^, Iran A va (p, tren B)

4. Bo qua xen phii don phan tii trong cac tfch phan trao ddi vdi Idi ciia cac
nguyan tu khae.

5. Coi cac yen td ma tran cheo Idi lian quan den hai nguyan tu ty le vdi cac
tfch phan xen phii tuong ung

Nang lugng electron tdng cdng ciia phirong trinh Roothaan qua cac phep
gan diing cd tha coi la tdng ciia hai thanh phan : thanh phan lien quan den mot
electron E, va thanh phan lian quan den cap electron E^R

Cung vdi sir phat trian, sir tham so hoa trong phuong phap CNDO cho ra ddi
Ciic phien ban CNDO/1, CNDO/2 . Trong hai phuong phap nay, phian ban
CNDO/2 cd quan diem rat gan vdi phuong phap sau la phirong phap INDO.

1.32.3 - Phirang phap INDO ( Intermediate Neglect of Differential Overlap )

</div>
(22)<div class='page_container' data-page=22>

Phuong phap nay la phuong phap ban kinh nghiem do Pople. Beveridge va
Dobosh dua ra. Trong tfnh toan, phuong phap gian tiep bo qua cac vi phan phii.
Nhu vay nd uu viet hon phuong phap CNDO a chd cd tfnh den cac lire day bat ky 
giia cac electron tren ciing mot nguyan tu. Phuong phap na\ dugc ap dung de tfnh
loan cac tfnh chat cua electron trong cac he vd ddng va vd mo, tdi uu hoa hinh
hgc va nang lugng tdng cdng.

Nhu ta da biet, theo quan diam phuong phap CNDO khdng phan biet tuong
lac giiia hai electron cd spin song song hoac ddi song, dac biet khi chiing ciing
nam trong mot nguyan tu. Do tfnh phan doi xiing ciia ham sdng, cac electron cd
spin song song khdng the chiem cung mot d, va do dd hai electron 6 hai AO trong
cung mot nguyan tu se cd the nang tuong tac day trung binh nho hon neu chiing

cd spin song song. Va mat loan hgc, diem khae nhau na\ dugc coi nhu xet lich
phan trao doi hai electron cd dang :

(/vu|H= JK0K(2)-^, OM (2) (^^^) n.32)

' 1 2

Trudng hgp la xet 0 day O^, Ou cung thugc mot nguyan tu. Phuong phap
CNDO bo qua cac tfch phan cd dang nay | 2 4 | va thay tai ca cac tfch phan giua
hai electron tran ciing mot nguyan tir bang y ma khdng ka den spin ciia chiing. Do
dd Ccic ka'l qua tfnh loan theo phirong phap CNDO khdng cho la biet sir tach trang
thai. Ngoai ra, do qua trinh trung binh hoa sir tuong tac xen phii ciia hai electron
Iran Cling mot nguyan tii, phuong phap nay khdng tha giai quyet dugc van da tach
trang thai trong cung mot cau hinh.

PhucTug phcip INDO cd mot so sua ddi. giii lai cac tfch phan xen phii don
nguyen tu nhung chi \di cac tfch phan cd dang mot tam. Phirong phap nay thudng
dugc ggi la phuong phap gian tiep bo qua cac tfch phan xen phu.

</div>
(23)<div class='page_container' data-page=23>

Phuong phap nay dugc xay dung dua vao viec sua ddi phuong phap INDO
do Dewar dua ra lan dau tian vao nam 1969. Qua trinh tfnh toan trong phirong
phap nay la ap dung phuong phap trudng tu hgp. Su sua ddi o day la phuong phap
MINDO/3 diing cac tham sd phii hgp vdi thuc nghiem thay vi tap trung vao tfnh
loan mdt each chfnh xac. Phuong phap nay thfch hgp vdi cac ddi tugng la cac phan
tii chai huu CO Idn, cac cation, cac hgp chat polynilro. Cac ket qua linh loan da
mang lai cac thdng tin can thiet ve tfnh chai electron , sir tdi im hoa hinh hgc va
nang lugng loan phan.

Cling mot CO sd ddi vdi phuong phdp MINDO cd cac cai lien, dd la cac
phicn ban MlNDO/1, MINDO/2, MINDO/3|161. Phirong phap MINDO/1 lien
hcinh tham sd hoa de tfnh cac tfch phan mot tam, tfch phan day hai tam va tfch

phan tuong tac hiit giira hat nhan va electron . MINDO/1 coi tfch phan cdng huong
ciia mot electron la ham sd cua khoang each giua cac hat nhan .Phuong phap
MINDO/2 cai tien tham, coi tfch phan day Idi la ham so ciia khoang each giua
Ccic hat nhan. Phuong phap MINDO/3 la phirong phap trung gian giua cac phuong
phcip CNDO, INDO ca NDDO ( Neglect of Diatomic Differential Overiap ) trong
dd chi bo qua vi phan phii hai orbital d hai nguyan tu khae nhau. Phuong phap nay
sir dung cac bg ham co sd Slater - Zener. STO - 3G, 4 -31 G, 6- 31 G [ 14|.

1.3.2.5 - Phirong phdp MNDO ( Modified Neglect of Diatomic Overlap )

</div>
(24)<div class='page_container' data-page=24>

1.3.2.6-Phuangphdp AMI ( Austin Model 1 )

La phuong phap trudng tu hgp ban kinh nghiem dugc ap dung kha phd
bien hian nay [17]. Phuong phap nay la kai qua cua xiec cai tien phuong phap
MNDO, ap dung cho cac nguyan tu thude chu ky mdt, hai va ba ciia bang he thdng
tu^n hoan loai trii cac kim locai chuya'n tiep. Cung vdi phuongphap PM3. phuong
phap AMI nhin chung la phuong phap ban kinh nghiem chfnh xac nhat diing da
tfnh loan cac tfnh chai electron [17J, tdi uu hoa hinh hgc, nang lugng toan phan va
nhiet hinh thanh.

1.3.2.7 - Phirang phdp PM3 ( Parametric model 3 )

Phirong phap PM3 cung ka mot phirong phap ban kinh nghiem sii dung ihual
hKin Hi hgp. Phirong phap PM3 la sir tham sd hoa mot lan nua ciia phU(rng phap
AMI. Qua trinh tham sd hoa trong PM3 dp dung cho nhieu nhdm nguyen td thugc
nhdm chfnh, loai trii cac kim loai chuyan tiep [271.

1.3.2.8 - Phirang phdp ZINDO (Zerner's INDO )

</div>
(25)<div class='page_container' data-page=25>

ZINDO su dung chiing 1000 ham co so. Vdi cac phian bean Idn hon ZINDO cd tha

mo rgng gidi han ddi vdi phan tu gom 1000 nguyan tu thi hcam co sd dat tdi 4000.

TOM LAI

Di cd mot cai nhin tdng quat ve cac phuong phap gan diing chiing la lap

mdt so dd (trang 22 )Theo so dd nay khi giai phuong trinh Schroedinger ihudng
ngudi ta sir dung hai phep gan diing :

- Phep gan diing hau iTnh Bohr Oppenheimer
- Phep gan diing MO- LCAO.

1/ Neu khdng sir dung nhiing phep gan diing khae chiing la se cd phuong phap
khdng kinh nghiem AB- initio, edn ggi la phirong phap tfnh tu dau.

Uu diam cua phirong phap nay la cho phep xac dinh dugc tai ca cac tfnh
chai ciia phAn tu chi tu nhiing yen td chii yen cua bai loan nhu sd hat electron ,
dien tfch electron , so hat nhan, loai hat nhan ma khdng sir dung bai eii cac sd lieu
thuc nghiem nao khae.

2/ Khi sir dung den nhung phep gfin diing khae, da don gian bai loan la se cd cac
phucmg phap ban kinh nghiem. Cac phuong phap nay chia lam hai loai :

-I- Loai thu nhai danh cho tat ca cac electron hoac ft nhat cho nhung electron
hoa tri cua cac hgp chat vd co hoac hiiu co.

</div>
(26)<div class='page_container' data-page=26>

3 * 
3 
3 
-• ? > '

d (J3 
n 
O N 
o 
3 
-OQ

o

X 
n 
n 
n 
<

o = - ^

—^ oc — 
^ 3 
X -O^ ^ 
"C 3

-CD 
O 
-U
?. 
•g & 
w n 
3 n 
0-, o 
O

o 3 
3 o^

f ^

3

•fi 
3 
C 
&}
r> 
n 
o 
ST

1- >• — r^ 
S. n o

N S ^

5 ^

n 
n

'-»j r o

<ãĐ r 
S 2 =1

- • , -^ ' ^

o "" -*'

f :r, O 
3 a

. = 3

>

cr

5"

o '

2. 2. !2 
3 Đã i

^ 0 3

C n S^

5. ^;

-— o>

O 3 
: ; o o

• a;. 3

r, 00 
^ 3 "

fX fV
• c 13

diin
g
diin
g

i|

- Oppcnh
e
LCA
O

9

o 
X 
n 
OQ
a 
3 
3 
-3 * 
3 
OQ
Dd 
o 
3 
3

00 
c 
o 
3 
X 
• <
a. 
00

Q

n

> ^

o

H

O

> > ,

</div>
(27)<div class='page_container' data-page=27>

1.4- Doi tugng nghien cOru cua de tai

Cling vdi su phat trien cua hoa hgc hiiu co, tu lau cac hgp chat di vdng da
dugc nghian ciiru va ung dung trong nhiau nganh khoa hgc va ky thuSt khae nhau
ciing nhu trong cuge sdng. Ngay nay so cac hgp chat di vdng da vugt qua sd' cac
hgp cha't vdng carbon va khdng vdng. Hang nam cac cdng trinh vi cac hgp chai di 
vdng chiem qua nua cac cdng trinh khoa hgc vi hda hgc huu co dugc cdng bd' 
.Cac hgp chai di vdng ngay nay da dugc ap dung rgng rai trong cac nganh nhu hoa
dugc, san xuat thude nhugm, nghian cijru cac hgp chat cd hoat tfnh sinh ly va hoa
sinh. Tuy da dugc nghian cuu nhieu nhu vay, cho den nay cac nghian cuu vi mat 
ly thuyet cac hgp chai di vdng van edn han che'

Hgp chai cu tha ma chiing tdi khao sat la day hgp chat a,P - xeton khdng no chiia

nhan ihiophen vdi hai dang:

dang A :

X

c=c-c

o

II ^ s

o ^

dang B

Q

c-c=c

o ^

</div>
(28)<div class='page_container' data-page=28>

L4.1 Dac diam vi cau tnic cua hop chat khao sat (X-CMHQOS)

1.4.1.1 Nhan phenyl vd vi tri the para.

Theo ly thuyet MO, cau tao cua benzen la mdt he thong lien hop 6 electron
pi . He thong lian hgp nay lam cho benzen ban vung hon rat nhiau so vdi cac
cyclodien . Do cd sir lian hgp ma cac lien ket tao thanh vdng cd dd dai ddng dau,
toan bd phan tir khdng phan cue va nam tran mot mat phang. Do dai ciia cac lidn
ket trong cac hydrocarbon lian hgp ndi chung cd gia tri trung gian ciia cac gia tri
C-C va C=C trong he thdng cac hydrocarbon thdng thudng. Vf du nhu :

Lian ka'l/kieu phan tu Do dai lian ket A°

C-C/phan tu chua nd'i ddi lian hgp phang 1.512
C=C/Phan tu chiJa nd'i ddi lian hgp phang. 1.338

C-C /Phan tu benzen 1.395

Tu dd, sir thay doi do dai lian ka'l cung cho ta thay muc dd lian hgp ciia hgp
chai. Nang lugng cua phan tu benzen cd the coi la mdt ham cua dd dai liSn ka't.
Khi thay the mdt hydro trong phan tu benzen bang mdt nhdm the' X, nhdm the' X
se lam thay ddi loan bd sir phan bo ddng deu ciia cac electron pi trong ha thd'ng
lien hgp, qua dd lam thay doi tfnh chat hoa hgc, co che phan ung ciia pha tir. Theo
ly thuyet cd dien, ngudi ta chia sir anh huong khi cd su phan bd' lai mat dd electron
trong phan tu thanh hai loai hieu ung chfnh.

</div>
(29)<div class='page_container' data-page=29>

day hay hut electron . Tfnh cha't cua hieu ung la ft thay d6i theo chi6u dai mach v^
chi CO tac dung tren mach phang. D'ltu nay dugc giai thfch la do su lai hoa cua 
cac electron pi ciia cac orbital p nam tromg mot mat phing xac dinh, nd'u lidn kd't
lien hgp vai no nam khae mat phang thi khong thi tao thanh he co xen phu cure dai. 
Cac nhom the halogen, NR2 , OR cho hieu ung+C, con cac lien ket C=0,
-CH=NH,-CH=CH2 lai the hien hieu umg -C . Nhu vay doi voi mdt s6' nhom chuc,
CO hai hieu ung ngugc chi6u-I va +C nhu cac halogen.

De dac trung cho anh huong t6ng cgng cac hieu ung Hammet co dua ra
mdt dai lugng la hang so Hammet ky hieu la a . Cac nhom thd' co a > 0 nhom
the la hiit electron , cac nhom the G< 0 cho hieu ung day electron . Gia tri tuySt
d6'i o cho bid't muc d6 anh huong cua nhom the. Duod day la m6t vai gia tri ciia
hang so Hammet a cua mot so nhom the thudng gap :

Ten nhom the Gia tri hang so Hammet a

^NH^ -0.660
-OH -0.357
-0CH3 -0.268

-CH3 -0.17
-H 0.000

-F 0.060
-CI 0.227
-Br 0.232
-CN 0.660
-NO. 0.780

Hang s6' Hammet a dugc xac dinh tir bieu thuc sau

k

Trong do :

</div>
(30)<div class='page_container' data-page=30>

ko va k la hang sd can bang cua phan ung phan ly a trang thai khdng va cd 
nhdm the 6 cac vi trf meta hoac para.

p - he sd', khdng ddi dd'i vdi mot dang phan tii, dac trung cho miic dd nhay
cam ciia phan tu dd'i vdi cac nhdm tha.

loo A chfnh la su bien ddi kha nang phan ung ciia cha't khi cd mat nhdm

the'.

1.4.12 Nhan thiophen

Dd'i vdi qua trinh tfnh toan cac hgp chat di vdng bang cac phuong phdp ban
kinh nghiem, chiing ta gap phai hai khd khan chfnh la xu ly su phan cue ciia lian
kai a, va tim kiem cac tham so hgp ly. Dd'i vdi cac hgp chat chi chiifa H,C, ta coi
nhu cac lian kei sigma C-C la khdng phan cue, va do dd khdng lam anh huong da'n
cac nguyan tu canh chiing. Do dai lian kai don, ddi hoac kep ba cd the coi la khdng
ddi trong loan bd phan tu, diau nay da dang cho qua trinh tham sd hoa. Dd'i v6\ cac 
hgp cha't di vdng , cu the la nhan thiophen, vi nguyan td S cd dd am dien Idn hon
nguyan to C, nan lian ket sigma S-C bi phan cue, lam anh huong den toan bd ca'u
hinh electron cua he. Cac tham so va do dai lien ket , nang lugng lian ka't ciia di t6
va C ndi chung la khd tim kiem hon so vdi cac hydrocarbon. Thiophen la hgp cha't
di vdng chua mdt di to khdng bao hoa, chiing cd tinh cha't khae vdi cac
xyclopentadien, va chiing cd tfnh chat lian hgp rd ret .

</div>
(31)<div class='page_container' data-page=31>

khdng tham gia vao he lian hgp, tro thanh nhdm cd kha nang day electron trong
phan tu. Hai vi trf 2 va 5 trong vdng thiophene cd kha nang tham gia cac phan ung
the electrophin nghTa la cd kha nang hiit electron . Trong trudng hgp khdng c6 
doan mach -CH-CH2CO thi vi trf so 2 se cd tfnh chat hiit electron . Viae cd mat
nhdm CO va nhan phenyl chua nhdm the paa X se cd tha thay ddi mat dd electron
cua C2 va C5 .va mat nang lugng , cac hgp chat di vdng thuong kem ban hon so
vdi benzen ;

Tan

AH

kcal/mol

769

507

578

612 Nang lugmg 6n dinh

kcal/mol

37.9

16

11

Benzen
Furan
Pyrrole
Thiophene

Trong ba hgp chai tren thi thiophen cd sir phan bd dien tfch dn dinh hon ca.
Dd dd thiophen cd do ben hon , khi tham gia cac phan ling hoa hgc. So vdi furan va
pyrrole thi thiophen la dugc coi la khd mo vdng hon ca.

Tliiophen trong cdng nghiep dugc diau che bang each ddng vdng butan,
butadien hay buten vdi S [8], phan ung thudng dian ra khi ta dun hdn hgp tai 600
oC, phun qua dng phan ung rdi ngung lai

1.4. J .3 Nhom Carbonyl vd sir dich chuyen electron trong mach lien hap :

Trong lian ket cua nhdm chiic Carbonyl C=0, nguyan to O cd dd am dian
Idn hon do dd se hiit electron vi phfa minh, lam cho lian ket n bi phan cue, nhd su 
lian hgp vdi nhdm C=C ma anh huong den nhan phenyl ddi vdi ca'u dang :

</div>
(32)<div class='page_container' data-page=32>

Sir lien hgp nay cung dong thdi anh hirdng den sir phan bd
cetron trong nhan thiophen.

dt each tuong tu la ciing cd buc Iranh lian hgp cua phan tu kiau B :

lai mat dd

^^.r^'^^

Nhu the rd tang nhdm C = 0 true tiep anh hirdng deii nhan phenyl va lan
jyan anh huong cua minh qua C=C den nhan thiophen.

Trong phan tu ma chiing Idi khao sal, cd ba lien ket don cd tha tao cac gdc
)an, gdc van, neu phan tu khdng ddng phAng, ihi sir dich chuyan electron trong

ach lian lurp lulu nhu Irict ticu.

Nhdm the X d vi ti i the para do dd hfiu nhu khdng cd tuong tac true tid'p vdi
idm the CO , ngoai ra o vi tri para nay hieu ling khdng gian cd tha bo qua.
guyan tu O cd tha cd cac tucrng tac vdi S trong nhan ihiophen d dang A:

c=c-c

II

o

^ S "

a lam cho phAn lir kcni ben hon.

Mat dd electron cd ihC tflp trung d nguyen t li O va nguyfin tir S. Nhdm tha'

. anh hucmg len nhan phenyl, do dd anh hirdng deii mat dd electron ciia nguyan tir 
K mat dd electron tai cac lien kai C = 0 , C=C . Cac vdng Ben zen va thiophen cung 
I bi anh hirdng. Ddi vdi mdi lian kai mat do electron cang cao thi do dai lian ka't

ang giiini.

</div>
(33)<div class='page_container' data-page=33>

khdng tham gia vao he lian hgp, tro thanh nhdm cd kha nang day electron trong
phan tir. Hai vi trf 2 va 5 trong vdng thiophene cd kha nang tham gia cac phan ung
the electrophin nghTa la cd kha nang hiit electron . Trong trudng hgp khdng cd
doan mach -CH-CH.CO thi vi trf so 2 se cd tfnh cha't hiit electron . Viae c6 mat 
nhdm CO va nhan phenyl chiia nhdm the paa X se cd tha thay ddi mat dd electron
cua C2 va C5 .Ve mat nang lugng , cac hgp chat di vdng thudng kem ban hon so
vdi benzen :

Tan

Benzen
Furan
Pyrrole
Thiophene

Trong ba hgp chai Iran thi thiophen cd sir phan bd' dian tfch dn dinh hon ca.
Dd dd thiophen cd do ban hon , khi tham gia cac phan ung hoa hgc. So vdi furan va
pyrrole thi thiophen la dugc coi la khd mo vdng hon ca.

Tliiophen trong cdng nghiep dugc diau che bang each ddng vdng butan,
butadien hay buten vdi S [8], phan ung ihudng dian ra khi ta dun hdn hgp tai 600
oC, phun qua dng phan ung rdi ngung lai

1.4.1.3 Nhom Carbonyl vd sir dich chuyen electron trong mach lien hap :

Trong lian kai cua nhdm chiic Carbonyl C=0, nguyan td 0 cd dd am dien
Idn hon do dd se hiit electron ve phfa minh, lam cho lian ket % bi phan cue, nhd su 
lian hc;rp vdi nhdm C=C ma anh huong den nhan phenyl ddi vdi ca'u dang :

AH
kcal/mol

769
507
578
612

Nang lugng 6n dinh
kcal/mol

37.9
16
16
11

X

</div>
(34)<div class='page_container' data-page=34>

Su lien hgp ni\\ cung dong thdi anh lurang den su phan b6' lai mat dd 
electron trong nhAn thiophen.

MOt each tuong tu ta cung co buc Iranh lien hgp cua phan tu ki6u B :

c-c=c ^

^6 ^

Nhu the rd tang nhdm C = 0 true liep anh hirdng den nhan phenyl va lan
Iruyan anh huong ciia minh qua C=C dan nhan thiophen.

Trong phan ui ma chiing Idi khao sat, cd ba lian ket don cd tha tao cac gdc
xoan, gdc van, neu phan tii khdng ddng phang, thi sir dich chu}'an electron trong
mach lian hgp hAu nhu iricl lieu.

Nhdm the X d \i tii the para do dd hfiu nhu khdng cd tuong tac true tia'p vdi 
nhdm the CO , ngoai ra d vi tii para nay hieu ung khdng gian cd th^ bo qua.
Nguyan lir () cd the c() cac tucrng lac vdi S trong nhan thiophen d dang A:

X

c=c-c

II

o

s"

va lam cho phAn lii kem ban han.

Mat do electron cd tha tap trung d nguNcn t li O va nguyen tir S. Nhdm thS'
X anh lurcmg len nhan phenyl, do dd anh hudng den mat dd electron ciia nguyan tir
O, mat dd electron lai cac lien ket C = 0 , C=C . Cac vdng Ben zen va thiophen cung
se bi anh huong. Ddi vdi mdi lien kai mat do electron cang cao thi do dai lian ka't
Ciing giam.

</div>
(35)<div class='page_container' data-page=35>

+ Dao dong C-C , Vc.c vao khoang 1100 - 1250 c m ' [11], su lien hgp se la
tang bac cua cac lien ket don va do do tang gia tri v.

+ Dao dong C=C ,Vc=c vao khoang 1600 den 1670 cm"', su lien hgp se lam
giam bac lien ket do do v^^c se giam xuong khoang 1600 - 1640 cm"'

+ Dao dong hoa tri C-H, ,VC.H vao khoang 2900 - 3300 cm"'
Cac dao dong bien dang 5C.H phu thugc manh vao nhom the .

+ Dao dong C-X tang theo do am dien cua nhom the X [6] vi du :

X v(cm"')
i 500
Br 500 - 600

CI 600 - 800

F 1000-1400

Dao ddng C=0, v,^^^ phu thugc rat nhiSu vao nhom R lidn ket vori C, vi du d6'i voi
hgp chat RH(C=0)

RH (C=0) Vc=o(cm"')
hgp chat no ( aldehyde, acid,cetone) 1700 - 1750

</div>
(36)<div class='page_container' data-page=36>

CHLONG 2: PHAN THLC NGHIEM VA BIEN LUAN

KET QUA

2.1 Phan mem va cac budc tien hanh nghien ciiru :

Nhu da nau , phuong phap AB- initio la phuong phap cd the mang hii do
chfnh xac cao nhai, nhung phuong phap nay ddi hoi qua nhieu thdi gian va dung
lugng may tfnh Idn de thuc hien qua trinh linh loan. Cac phuong phap ban kinh

nghiem cd tung do chinh xac riang cua nd tuy thude vao sir phii hgp ciia cac tham
sd va dieu kien hdi tu dua ra trong qua trinh thuc hien tinh toiin theo dai thuat
Irudng tuhgp SCF. Vi du nhu vdi che do hoiit ddng chuan ciia MOPAC [13].

Phuong phiip Do dai( A") Gdc liankai ( ") A H ( kcal/mol)

MIND03 0,001 0.1 1
AMI 0.01 1

PM3 0.036 3.9 4.4-10

Hien nay Iran the gidi phat hanh rat nhiau cac phan mam cho phep ta giai
cac bai loan theo ca hai phuong phap AB- initio va cac phirong phap ban kinh
nehiem.

*-Phrin mem cho phep chiing ta khao sat phan tu d cii trang thai hoi va trang
thai dung dich, o trimg thai vd ddng hoac trang thai vd md ( trang thiii kich thich ).
0 ban luan van nay. chung tdi sii dung phan mem HYPERCHEM phian ban 4.5
ciia cdng ly HYPERCUBE Inc. Vi day la phan mem da sir dung , cd san va cd do
chinh Xiic phii hgp da thuc hien nhiem vu dat ra.

</div>
(37)<div class='page_container' data-page=37>

dat cue tiau so vdi cac lan can dugc khao say [20]. dieu kien kai ihiic : 0.1 kcal/(A''
mol) ( su bien ddi nang lugng theo ba true X, Y, Z )

Trong phep tinh Single Point, khi su dung phuong phap AMI, chiing tdi sir dung
cac diau kien :

Dien tfch = 0. Tdng so Spin = 1.

Diau kien hdi tu :0.00lkcal/mol.

So vdng lap tdi da trong thuat loan trudng tu hgp : 150.

Trang thai kfch thfch cua cac electron hoa tri trong phan tii : thap nhai.
Cap ddi Spin : phuong phap UHF ( Unrestricted Hatree Fock ).

Khi sir dung phuong phap tfnh Single point bang phuong phap ZINDO/S :
He sd sua ddi ddi vdi cac tfch phan cdng hudng [5,j ;

</div>
(38)<div class='page_container' data-page=38>

2.2 Cac birdc chung toi tien hanh tinh toan khao sat co the bao gom

TT Noi dung Ghi chii

01 Dung cac c^u hinh co the d6'i vai hai dang alpha( A) va be ta
(B) l6'i iru hoa hinh hoc bang phirong phap AMI

8 thi nghiem \ai S ciiu dang

02

03

04

06

Lua chon phuang phap theo nang lucmg lien kei. nhiei hinh

thanh doi vai 1 phan tu.

Cac phuang phap su dung : CNDO. INDO, MINDO,
MINDO/3, AMI, PM3. ZINDO. ZINDO/S.

Tim cau dang ben nhat A va B . xac dinh cac thong so hinh
hoc ph^n tu. gian do spin, electron ciia phin tir

Theo ca hai phuang phap ZINDO/S va AMI

8 thf nghiem, ket luan :

-tinh loan E.Delta H, : phuang
phap ZINDO/S

-Tinh toan momen luong cue/ pho
dao dong : phuang phap AMI

Khao sat su keo dai mach :
Ben/en
C6H.S-CH3
C6H5-C2H3
C6H5-C2ir^-rHO
C6H.'S-C2H3-CO-C6H5
A4
B2

X thf nghiem toi uu hoa hinh hoc
bang phuang phap AMI

8 thf nghiem bang phuang phap
ZINDO/s

8 thf nghiem bang phuang phap
AMI

Kei luan Phan tu B2. A4.

T6\ uu hinh hoc phan tu A4-X va B2-X trong do X la cac

nhom the :

NH2,OH.OCH3.CH3,HT.Cl.Br.CN,N02

5 thf nghiem loi mi hoa hinh hoe

bang plnnrng phap AM I.

7 T\^\ nghiem hang phuctng phap 
ZINDO/s

7 TTif nghiem hang phuang phiip
AMI.

7 thi nghiem hang phuang phap
PM3

20 thf nghiem vai phan tu A4-X
va B2 X hang phuang phap AMI

Ti'nh loan cac thong so luang lu nhu nang luong lien ket,
nhiet tao thanh. momen luong cue. cac thong so hinh hoc
phan tir cua cac phan lir .A4-X va B2-X

56 thf nghiem vai phuang phap
ZINDO/S ( nhom the -Br va -CI
khong Ifnh dugc bang phuang
phap ZINDO/S. Tfnh moment
luang cue bAng phuang phap
PM3

07 T'nh loan dao dong ciia nguyen tir trong phan lir . pho hong
ngoaiilR) cua cac phan lir A4-X va B2-X .

T6ng cong so ihi nghiem

IX thf nghiem bang phmrng phap
AMI

</div>
(39)<div class='page_container' data-page=39>

2.3 Chon phirong phap.

Nhir da neu a phdn trdn, hien nay co r^'t nhieu phuong phap tinh gan dung. De bat 
dau khao sat anh hirong cua cac nhom the len day cac hop cha't a,p xeton kh6ng no
chiia di vong thiophen, chung t6i ti^n hanh tfnh thu theo cac phuog phap hien co de
tim ra mot phucmg phap tfnh phii hop.

Cac phuang phap tfnh gan dung nay cho cac bo cac ket qua khae nhau. Ngoai ra,
d6i voi tung day cha't cu the, se co cac phuong phap phu hop .Ta biet rang trong

phien ban HYPERCHEM 4.5 co t6n tai tam phuong phap tfnh gdn dung, trong do

hai phuong phap ZINDO/1 va ZINDO/S khdng co kha nang t6'i uu hoa hinh hoc va
phan tfch dao d6ng. Dua vao lich su phat trien cac phuong phap, ddu tien chiing
t6i th6ng nhat sir dung phucmg phap AMI de toi uu hod hinh hoc phan tir. Phan tir
duoc diing de khao sat va xac dinh phuong phap tfnh la phan tir Al, co dang :

Sau do Idn luot sir dung tam phuomg phap de tfnh toan cac thong sd tuong
tir. Cac thong s6 : nang luong lien ket, nhiet hinh thanh va mdment luong cue. Ket
qua thu duoc dugc thong ke trong bang 2.1, va bieu dien bang bieu do 2.1, 2.2 .
Cac ket qua tfnh toan cu the luu o phdn phu luc I.

Bang s62.1 : Ket €^^4phafttich-ItfechoA phuong phap
Phtftnig
phap
CNDO
INDO
MNDO
MIND03
FM3
Naf>fi lui;nig
k>an phdn
(kcal/mol)
-80752.175
-78299.631
54235.24^
--53880.007
-50083.121
Occal/mol)
-H349-.5-28
-8111.915
-2K2I.K09

-2814.190
- 2 8 1 9 ^ 3

</div>
(40)<div class='page_container' data-page=40>

AMI
ZINDOL
ZINDOS

-53384.192
- 7 4 1 3 5 ^ 6
-63067.884

-2825.255
-8325^81
-10837.482

-288856.707
-334953.313
-261849.807

43.294
-5456.732.
-7968-933

2.958
6.147
7.259

nhj^t h'mh th^h

( kcal/mol )

NHlfeT HINH THANH

-8000
-6000
-4000
-2000
n
2000

f-

" • " fl'

fl fl • fl

/ - • ^ ^ " • B I F iflP JHP iSP iflP v ^ ! ^ 1 
• • • • . • • • ^ • • r . i . . i . ^1111.1 M.,ini».n.Mi|"

-i -i -i 8 1 1 8 8

O - 5 ? ? Z 
5 N r^ 
phiroDg ph^p

Biau d6 2.1 : Sir phu thu6c cua nhiet hinh thanh vao phiiorng phap tmh

Nang lUfWig li*n 
k6i {kcalAnol )

NANG Ll/ONG LifiN k f T

o

ontr

CO CO ^

S ^ s

Z O Q- <

Bie\i d6 2.2 : Sir phu thuoc ciia nang laong lien ket vao phircmg phap tfnh

</div>
(41)<div class='page_container' data-page=41>

cac qui luat cua nhiet hoa hoc. Phuong phap ZIXDOl. CXDO. IXDO mac du cho

ket qua nang lircmg toan ph^n nho nhat nhung cac gia tri ve nhiet hinh thanh va
nang lucmg lien ket lai lan han so voi cac ket qua tfnh bai phuomg phap ZINDO S.

Va moment luong cue, dua vao cac tai lieu da duac cong bo |31|,[32] ,
chiing toi ket luan phuang phap PM3 cho ket qua phii hop hom ca (3.122 D ).

Tu cac ket qua thu dugc da cho phep chiing toi di den quyet dinh chon cac
phuang phap tfnh cho day xeton khong no chiia di vong thiophen X- Cj^HgOS nhu
sau : Toi uu hoa hinh hoc bang phuomg phap AMI, tfnh toan cac thong so nhu
nang lugng lien ket , nhiet hinh thanh bang phuang phap ZINDO/S va tfnh toan gia
tri moment luang cue bang phuang phap PM3.

2.4 Phat trien mach

Da CO tha hiau ro han phan tu xeton khong no chua di vong thiophen,
chiing toi ticn hanh khao sat sir phat trien mach , bat dau tir phan tu Bcn/cn den
phan tu B2.

Thong qua qua trinh khao sat sir phat trien mach, chiing toi muon xac dinh
su bien d6i vi cau hinh electron cua phan tu, sir anh huong cua doan mach keo dai 
den vi trf H^^.^ , vi trf ma chiing toi khao sat vai cac nhom the khae nhau, Ngoai ra
chiing toi ciing muon nghian cuu vai tro cua di vong thiophen doi voi phan tu khi
chua CO mat cac nhom the.

Cac ket qua dugc thong ka trong bang 2.2 , nang lugng lien ket va nhiet
hinh thanh dugc biau dian tran bieu do 2.3a, 2.3b.

Bang 2.2: Ket qua tfnh cho day chat nghian ciiii :

l*h;»n III
CeHe
CeHsCHs
CeHjC^H^
CeHjCrHjCHO
CeHsCjH^COCeHs
A4H

M litn kei
-4860.71
- 5 9 2 4 35
- 6 4 5 4 90
-7557 58
- 1 2 1 5 5 0 3

-1084540
Nhiet hi
-3522.76
-4311 31

-4670 96
-554320
-8906.90
-7976.85
d,:
2494680
2,493170
2 493370
2,493370
2493170
2493280

M "

P.r-0.019
0 0 1 8
0 131
0 135
0 135
0 230

M C" p,,.
-0,019
-0.030
-0 127
-0 111
-0,113
- 0 0 1 2

q O

-0 2 9 5
-0 307
- 0 5 4 1

</div>
(42)<div class='page_container' data-page=42>

B2H 10853,14 -7984 59 2 494240 0 230 -0 003 -0 525 3,158

Oday :

+ Nang lugng lian ket va nhiet hinh thanh tfnh bang phuang phap ZIXDO/S
theo don vi kcal/mol .

4- di2 la ky hieu khoang each giira nguyen tu H gan vao vi tri alpha den tam
cua goc phenyl.

+ q la dien tfch dinh cu tren nguyen tu trong phan tu.

+ |J.(D) la moment luong cue tfnh bang don vi D theo phuong phap PM3

Mingliitiiglieiiket
-14000.00

-i3ajo.oo
-iajoo.oo

^ -XOflKDj

J -6tjoo.a)r

:i -imsi)

QQ) X X 
X

Fhm nV

</div>
(43)<div class='page_container' data-page=43>

o 
E

"TO

o

Nhiet hinh thanh

9000.00
8000,00
7000 00
6000,00
5000.00
4000,00
3000 00
2000 00
1000 00
0.00 J

A

y ^\-'~m

. v~

'^

P

_ |

—

___

-...

-]

ph^n tir

Bieu db 2.3b: Sir phu thugc cua nhiet hinh thanh vao day chat nghien cuu.

Dua vao cac ket qua tfnh loan, la nhan thay cac gia tri vc nang lugng lien
ka't va nhiet hinh thanh luan theo qui luat cua nhiet hoa hgc, tang theo so lian ket
va do keo dai mach, phu thugc vao ban chat cua nguyan tu .

Kfch thuoc hinh hgc ciia nhan phenyl hau nhu khong bi bien doi do su keo
dai mach, dieu nay giiip ta tian doan mot ket qua tuong tu doi voi qua trinh khao
sat phan tirX-C,,H,OS.

</div>
(44)<div class='page_container' data-page=44>

C ta nhan tha'y sir anh huong dang ke cua di vong thiophen khi thay the vong
benzen.

D6'i vai c6ng thuc phan tu C,, HjoOS cua hgp cha't a,|3 -xeton khong no chua di
vong thiophene , chiing toi dua ra 8 cau dang co tha tuong limg voi hai ddng phan
nhu s a a :

Phan tu Al Phan tu A2

</div>
(45)<div class='page_container' data-page=45>

J,

( ) " •

-r

J 1

.,-**

^

9

'<^'

j .

1

r

t

Phan tu B Phan tu B2

Phan tu B3 Phan tu B4

</div>
(46)<div class='page_container' data-page=46>

Cac ket qua tfnh toan dugc thong ke trong bang so 2.3. Gia tri nhiet hinh
thanh va nang lugng lian ket dugc biau dian trong tran bia'u do 2.4a, 2.4b, 2.4c,
2.4d

Bang 2.3 : Ket qua khao sat - lira chgn cau hinh ban nhat

Doi voi phan tu kieu A

Dong phan NL loan ph^n
( kcal/mol )

NL liiin ket
( kcal/mol )

-10837790
•10840.228
•10845 142

-10845.396

Nhiil't hinh thanh

( kcal/mol )

-7969.241
-7971.679
-7976.593
-7976.847 
M 
(D) 
3.639
3.266
2.642
3.122 
A l
A2
A3
A4
-63068192
-63070630
-63075544 
-63075.798

Doi vdi phan tif kieu B

Dong phan NL loan phdn
( kcal/mol )

NL lien kci
( kcal/mol )

Nhici hinh ihiinh

( kcal/mol )

Nhiet hinh thanh

ro
o
-7978
-7976
-7974
-7972
-7970
-7968
-7966
-7964

^ ^ - " ^

''—n—

1

—

A1 A2 A3 A4

cau dang
M
(D)
BI
B2
83 
B4
-63082 723
-63083.541

-63068991
-63072.707
-10852 321
-10853.139 
-10838,589
-10842.306
-7983.772
-7984.590 
-7970,040
-7973.757
3.002
3.158 
2642
3.005

</div>
(47)<div class='page_container' data-page=47>

Nhiet hinh thanh

-7978
^ -7976

o -7974
E -7972
ro -7970
^ -7968
— -7966

-7964

/ ^

A1 A2 A3 A4
cau dang

Bieu do 2.4a : Quan he giua hinh tao thanh - Cau dang kieu B

Nang Luang li^n k^'t

-10846
— -10844

O -10842
E -10840 
^ -10838
^ -10836
^ -10834 f

-10832

Al A2 A3 A4

Ca'u dang

Bieu do 2.4c : Quan he nang lugng lien ket - cau dang kieu A

Nang lugng lien ket

-10855

O -10850
E -10845

"TO -10840

^ -10835
-10830

B2 B3 B4

Cau dang

</div>
(48)<div class='page_container' data-page=48>

Theo cac ket qua tfnh toan dugc , trong day cau dang A, p h ^ tu A4 co
nang lugng lian ket va nhiet hinh thanh cue tieu. Tuong tu nhu trong day ca'u dang
B , phan tu ban nhat la phan tir B2. Ta co tha nhan thay qua bang biau dian cac
phan tu trong kieu cau dang A khong khae nhau rS't ft so vdi kiau eSu dang B ,
ngoai tru gia tri moment luong cue, do chanh lech cac gia tri 16n nha't va nho nhat
cua cac dai lugng dugc thong ka trong bang 2.4 :

Bang 2.4: Do chanh lech giua cac gia tri lorn nhat va nho nha't cua hai kia'u ca'u
dang

Nang lugng Nang lugng Nhiet hinh moment luong
toan phan lian ket thanh cue (D)
( kcal/mol) ( kcal/mol) ( kcal/mol)

Cau dang A
Ca'u dang B

'^B2-A4

7.606
14.55
-7.743

3.167
2.964
-0.203

</div>
(49)<div class='page_container' data-page=49>

, >

-V

Hinh 2.1 : Thdng s6' hinh hoc phan tir A4

Cac th6ng s6 hinh hoc chfnh:
Kfch thiroc nhdn phenyl ( A")
C1-C2

C2-C3
C3-C4

1.39757

1.39815
1.39387

C4-C5
C5-C6
C 6 - a

1.41089
1.40747
1.39497
D6 dai lian ka't tiir tam nhan phenyl dd'n H vi tri para : 1.796345 A".
D6 dai lien ka't C7=C8 : 1.35203 A°,

66 dai li^n ket C = 0 : 1.2444.9 A°

Goc va»: C6^- C5 -C7-C8-: -a752772 °
Goc vaii: C7 - C8 - C9 - CIQ: +0.777739 "
Goc van: CIO - C9 - CI& - C19 : a793954 °

Dian tfch O :-0.541 ( Quyat dinh tfnh phan circ cua phan tir)
Trong luong phan tir: 416 g/mol

Chiau dai toi da ciia phan tir: 12.00 A°.

</div>
(50)<div class='page_container' data-page=50>

V^" "V

'--'\.

Hinh 2.2 :Th6ng s6' hinh hgc phan tu B2
Cac th6ng s6' hinh hgc chfnh

Kfch thudfc nhan phenyl ( A'')

C1-C2

C2-C3
C3-C4

1.39486
1.39523
1.39318

C4-C5
C5-C6
C6-C1

1.410251
1.39971
1.39404
D6 dai lian k^t tiir tam nhan phenyl den H vi tri para : 1.79722 A^

Do dai lian ket C7=C8 : 1.35203 Ao, dd dai lian ket C=0 : 1.24419 A* 
Goc van: C6-- C5 -C7-Ca • -a2L714 °

Goc vaii; C6 - C5 - 07 - Ci4^ L5X282 °
Goc vaii: C5 - C7 - C8 - U S : 4 3 ^ 5 9 °

Dian tfch O :-0.541 ( Quyet dinh tfnh phan cue ciia phan tu)
Chiau dai t6i da ciia phan tu : 10.8 A°

Dian tfch riang cua phan tu : 45 A""^.

</div>
(51)<div class='page_container' data-page=51>

Dua vao cac diJ lieu thu dugc nhu tran ta nhan thay kfch thude ciia nhan

benzen khong thay d6i khi co nhom tha' trong hai phan tu A4 va B2. Kfch thude
cua nhan thiophen trong hai phan tu A4 va B2 sau khi da tdi uu hoa hinh hgc cung
khong thay d6i so vdi phan tu thiophen .

Su phan bd electron cua hai phan tu khae nhau ro ret. Trong phan tu A4,
nhd dong phang ma nhom C = 0 phan cue keo theo su phan cue ro ret ciia lian ket
C=C. Ddi vdi phan tu B2 do phan tu khong ddng phang nan kha nang lian hgp kem
di ro ret, do vay anh hudng cua nhdm C = 0 lan nhdm C=C kem di nhieu, dieu nay
the hien qua dien tfch dinh cu tran hai nguyan tu C=C. Mot diam can chii y la neu
lay hai nhan benzen va thiophen lam mdc thi sir loi keo electron cua nhdm C = 0
tran hai phan tu la ngugc chiau nhau. Diau nay ciing keo theo sir thay ddi phan bd
electron trong nhan thiophen va nhan benzen dac biet la vi iri para. Dien tfch dinh
cu trong tran hai nguyan tu C va H tai vi trf the para trong phan tii A4 la
0.012/0.023, trong phan tu B2 la 0.003/0.023 con trong phan tu Benzen la
-0.019/0.019.

2.5 Anh hufdng ciia cac nhom the para-X-phenyl thugc phan tii A4X va B2X :

Trong phan trudc , chiing ta da thao luan va hai kieu phan tu A4 va B2.
Bang each phan tfch sir keo dai mach ciia phan tu, ta da xac dinh dugc vai tro ciia
tung thanh phan cau triic cua phan tu. Bang tfnh toan lugng tu, chiing toi da dua ra
mot each dinh lugng cac hieu ung xay ra trgng toan mach phan tu. Trong phfm
nay chiing toi thao luan ve anh hudng ciia nhdm the ddi vdi phan tu. Cac nhdm
the ciia chiing loi bao gom ( Sap xep theo sir tang hang sd Hamet ! 1 ) :

NH,

-0.660

OH

-0.357

OCH,

-0.268

CH,

-0.170

H F CI Br

0.000 0.060 0.227

CN

0.232 0.660

1

NO2

0.780

</div>
(52)<div class='page_container' data-page=52>

Cac phan tu RCl, RBr ( R=A,B) khong tha xac dinh dugc cac thong sd nhu nhiet
hinh thanh , nang lugng lian ket, nang lugng toan phan bang phuong phap
ZINDO/S do han che cua phuong phap.

Khi cac nhdm the dugc the vao vi trf para ciia nhan phenyl thi hieu irng
khong gian dugc coi la khong dang ke .

De xem xet anh hudng cua cac nhdm the tai vi trf p- phenyl trong phan tu
a,p - xeton khong no di vdng thiophen den su phan bd lai mat do electron chiing 
toi tien hanh tfnh cac tham sd lugng tu sau day :

+ Nang lugng toan phan, nang lugng lian ket, nhiet hinh thanh.

+ Mo men luong cue.

-f- Khoang each ciia nhdm the vdi tam vdng phenyl.

+ Dien tfch dinh cu tran cac nguyan tu O, S, C khi cd mat ciia nhdm the X
d vi trf para.

+ Phd hong ngoai IR ( hay dao dong cua mot sd nhdm chue quan trgng nhu

V c = 0 . V c = c . Vc.M ngoa. ma. ph^ng VcH=CH trans )• R i c H g d o i v d i p h 6 h o U g U g O a i , c h l i u g t o i c h l

khao sat trong moi trudng don phan tu (chan khong ) khong chiu tac dong ciia cac
yeu td ban ngoai nhu trudng luc hay trang thai nhiet dong.

Cac ket qua tfnh toan dugc trinh bay dudi dcang bang, bieu dd va dd thi. Cac
ket qua chi tiet dugc ghi lai theo cac file , tan file va ngi dung chfnh dugc luu
trong phan phu luc .

Bang 2.5 : Cac tham sd lugng tu tfnh dugc cho phan tu kia'u A4X

Nhom the
-NH2
-OH
-0CH3
-CH3 
-H
-F
-CI
-Br
-CN

-N02
Hang so
Hamet
-0.660
-0.370
-0.270
-0.170
0.000
0.060
0.227
0.232
0.660
0.780
Nang Nang
lucnig TP luongLK
-69097.06 -11827.67
-70737.53-11467.50
-75207.78 -12510.85
-67568.65 -11911.34
-63075.80 -10845.40
-73053.44 -11062.38
1 ! 
-71204.66 -11713.08
-83158.68 -12412.40
Nhiet
hinh 1
thanh
-8227.04
-8539.40
-9307.65

-8767.70
-7976.85
-8227.04
-8612.74
-9363.84

dl2 q S q O

2.83873 0.672661 -0.323871
2.78202 0.675140 -0.320955
2.78683 0.673980 -0.321521
2.90835 0.675499 -0.319613
2.51502 0.674000 -0.319180
2.77184 0.679743 -0.317682
3.10957 0.679746 -0.316730
3.29052 0.6X0694 -0.315636
2.83098 0.684538 -0.313540

2.89517 0.689573 -0.309316

</div>
(53)<div class='page_container' data-page=53>

Bang 2.6 : Cac tham sd lugng lir tfnh dugc cho phan tu kieu B2X
Nhom
the
-NH2
-OH
-0CH3
-CHS
-H
-F

-a

-Br
-CN
-N02
Hang sd
Hamet
-0.660
-0.370
-0.270
-0.170
0.000
0.060
0.227
0.232
0.660
0.780

Nang Nang Nhiet tao d,. q S q O
lugng TP lupngLK thanh

-69109.39-11840.01 -8806.36 2.82764 0.574107-0.300857
-70747.28-11477.25 -8549.14 2.77227 0.576395-0.295447
-75216.88 -12519.95 -9316.75 2.78019 0.573455 -0.294083
-64544.99 -8887.68 -5744.03 2.89819 0.575517 -0.291903
-63083.54 -10853.14 -7984.59 2.50390 0.575795 -0.290253
-73062.56-11071.50 -8236.16 2.76084 0.578774 -0.288756
1 ,3.09838 0.579097 -0.286816
I ! 13.27852 0.580457 -0.284657
-68063.15-8571.57 -5471.23 2.82764 0.582092-0.281361
-83166.37-12420.09 -9371.53 2.88176 0.588070-0.273255

MB2X !
3.913
2.286
4.243
3.367
3.158
2.933
2.938
2.930
3.810
5.238

dday :

+ Nang lugng toan phan, nang lugng lian ket, nhiet hinh thanh tfnh theo
phuong phap ZINDO/S , sau khi da dugc tdi uu hoa hinh hgc hang phuctng phap
A M I .

+ di2 la khoang each tii nhdm the den tam ciia vdng phenyl ( Sau khi tdi Uu
hoa bang A M I ) .

+ qS, qO la dien tfch dinh cu tran cac nguyan tu S, O cua phan tii da dugc
tdi uu hoa.

+ \.i - moment ludng cue tfnh theo don vi D , bang phirong phap PM3 
2.5.1 Anh hudng ciia nhdm the den NLTRNLLK, Nhiet hinh thanh :

Di xem xet mot each cu the anh hudng cua nhdm the den nang lugng lian

</div>
(54)<div class='page_container' data-page=54>

-90000.00 rT

-80000.00 J ^
-70000.00
-60000.00
-50000.00 K
-40000.00 f
-30000.00 i'
-20000.00
-lOOOO.OO
0.00

ID NLTP A4X
• NLTP B2X

OCH3 NO:

Nhom iha

Bieu dd 2.5 : Nang lugng toan phan phu thugc nhdm the

DNLLK A4X 
• NLLKB2X

-14000.00
-12000.00
-10000.00
-8000.00
-6000.00
-4000.00
-2000.00 K

0.00

OH (K-H3 CH} H

Nhom the

Bieu dd 2.6 : Nang lugng lian ket phu thugc nhdm the

I Nhiet

Nhiet

hinh thanh A4X,

hinh th.inh B 2 X |

Bieu dd 2.7 : Nhiet hinh thanh phu thugc nhdm the :

</div>
(55)<div class='page_container' data-page=55>

xet thi phan tu RNO2 ( R=A4,B2 ) ben nhat, the hien d cac gia tri nang lugng lian
ka't va nhiet hinh thanh.

2.5.2 Anh hudng cua nhdm the lan gia tri moment ludne cue :

Cac ka't qua thuc nghiem [31],[32] va ly tfnh toan theo ly thuyet dugc trinh bay d
cac bang sau :

Bang 2.7 : Gia tri Mo ment luong cue ( \ji ) thuc nghiam va ly thuyet cho cac dan 
xuat the para cua A4X va B2X

Nhom the'( -X)

NH2 
OH 
0CH3 
CHS 
H 
F 
CI 
Br 
CN 
N02 
HA4
TN 
4.450
3.900
3.405
3.150
2970
3.090
4.950
X(D)
LT
4.400
2.806
3217
3405
3 122
2514
2.666
2.635
HB2X(D)

TN
4.110
3710
3290
3.080
2700
2.920
3.333

4.941 4.860

LT
3.913
2286
4243
3 367
3 158
2933
2938
2930
3,810
5.238

LT va TN : gia tri tfnh toan bang ly thuyet va thuc nghiem [).

Cac ka't qua phan tfch tuong quan bang phan mem MS - EXCEL cho phan tu A4X
va B2X dugc ghi d bang sau day :

LT

TN

Phan tir A4X Phan xu B2X

LT

1 0.955435

TN LT TN

1 1 0.959736 1

</div>
(56)<div class='page_container' data-page=56>

Vdi ha sd tuong quan giiia gia tri thuc nghiem va ly thuyet ( - 95*^^) ta cd 
the ket luan phuong phap gan diing PM3 cho cac ket qua kha phu hgp \di thuc
nghiem

Dua vao ket qua tfnh dugc, neu loai trii gia tri u ddi vdi nhdm the -OH ta
nhan thay tuong quan giua gia tri |i va hang sd Hammet ddi vdi cac nhdm the cho
hai kiau phan tu A4X va B2X dugc chia thanh hai nhanh va dugc bieu dien tran
hinh sau :

e

E 
o

&.50Q I 
5 . 0 0 0 i

y = -1.966X + 2.995

g 000

y = 2.899X + 2 082

0 8 0 6 0 4 0 2 0 0 2 0 4

hang so Hammet

0 6 0 8

Hinh 2.3 Moment ludng cue ciia phan tu paraX-A4 phu thugc vao hang sd
Hammet

£ 
•o

6.000

-•0.8 -0.6 -0.4 -0.2 0 0 2 0.4 0.6 0.8
hang so Hammet

</div>
(57)<div class='page_container' data-page=57>

Dua vao bang ka't qua tfnh toan va dd thi, chiing toi cd nhung nhan xet sau day :

Ddi vdi ca hai kiau phan tu A4X va B2X momen luong cue tang theo su
tang gia tri tuyet ddi cua hang sd Hammet. Dieu nay cd nghTa la d vi trf para, mdt
nhdm the cang manh du day hay hiit cung se gay ra su phan cue Idn cho phan tu.

Su tang nay tuyen tfnh vdi gia tri hang sd Hammet ( na'u nhu loai trir cdc gia
tri tfnh ddi vdi cac phan tu p -OH- B2 va p-0H-A4 ),

Ddi vdi phan tu kiau p -OH- B2 va p-0H-A4, cac gia tri tfnh khdng tuan
theo trat tu . Diau nay cd tha do : ddi vdi kiau phan tu dang khao sat, hang sd
Hamet khong hoan toan dac trung cho nhdm the hoac phuong phap PM3 la
khong thfch hgp vdi kiau phan tu a,(5 xeton chiia di vdng thiophen.

Anh hudng cua nhdm the lan hai kieu phan tu A4X va B2X kha gidng nhau.
Trong dd nhdm chue CO dugc ndi true tiep vdi nhan phenyl cd nhdm tha' para
hay ndi qua nhdm vinyl. Diau nay khang dinh rang nhdm vinyl cd vai tro nhu cau
ndi lan truyan hieu ung lien hgp trong phan tu a,p xeton chua di vdng thiophene.

Vdi cung mot gia tri tuyet ddi cua hang sd Hammet a, nhdm tha' day
electron gay ra sir phan cue Idn hon cho phan tu. Diau nay the hian d dd ddc cua
hai nhanh cua dd thi:

Nhanh tgctA4x t g a B2X

Trai -1.966 -1.121
Phai 2.899 2.931

</div>
(58)<div class='page_container' data-page=58>

X

QOO

2^00

(00

y 2 = 0.8914X-0.2545

^A4X-|aA4H

• Series 1
• Series2

Chu ihi'ch

.Series 1; nhom ihe (Ja\ dien !ir
Scries 2: nhom ihO hul dien li'r

Hinh 2.5 : Moment ludng cue ciia hai kieu phan tii A4X va B2X bien doi iheo
nhdm the

Nhan xet : nhu hinh biau dian, neu nhu loai tru hai trudng hgp ung vdi
nhdm the -OCH:,, mdi quan he giiia sir bien ddi ciia moment ludng cue cd tha bieu
dian bang dudng thang.

</div>
(59)<div class='page_container' data-page=59>

Dudng thang hdi qui cua y2 nam tran yl chung td rang cac nhdm tha' hiit
electron gay ra su khae biet ve momen ludng cue giua hai kiau phan tir hon nhdm
the day electron .

Khi khao sat su thay ddi cua cac nhdm the, chiing toi edn khao sat anh
hudng ddng thdi ciia nhdm the lan hai dai lugng :

+ Moment luong cue

-h Khoang each tu nhdm the den nhan ciia vdng phenyl

De dac trung cho hai dai lugng nay , chiing tdi gia thiet mot dai lugng

D =

Trong dd P la cac gdc A4 va B2

Ka't qua dugc cho dudi dang bang sau

Bang 2.8 : Gia tri D phu thugc vao nhdm tha'

-X
NH2
OH
0CH3
CH3
H
F
CI
Br
CN
N02
Hang
s6'
Hamet
-0.66
-0.37

-0.27
-0.17
0.00
0.06
0.23
0.23
0.66
0.78
A4X

^ _ Mn - Mi'H

PX PH 
3.948
-2.794
0.350
0.719
B2X

r\ _ ^PX ~ ^PH

^PX ~ ^ PH

2.332
-3.249
3.927
0.530
-2.367
-0.767
-0.628

0.668
4.785
-0.876
-0.370
-0.294
2.014
5.505

chii thfch : D

dpx - dpH

{ tfnh bang Dobai/A"")

</div>
(60)<div class='page_container' data-page=60>

Na'u bd qua cac gia tri ung vdi nhdm the OH ( cung nhu trudng hgp khao sat nhdm
the anh hudng den momen ludng cue thi dd thi cd dang :

^ s

-0

n r ? sap^^BT— p. i

5 !

A

•

""^^ " ; y = 7 . 9 1 3 8 x 2 . 7 6 4

-^ -^ 9 _ -^ -^

^ ^ 1 ^^

.8 
y =

-0.6 
-8.4088X

-0.4 - 0 . 2 > w 6 Q Mr 0.4 0.6 
-1.5238 ' ^ ^ V ^

0.8

Hang so Hummet

Hinh 2.6 : Mdi quan he giiia D va a ddi vdi kiau phan tu A4X

Bd qua gia tri ung vdi nhdm the OCH, ta thu dugc dd thi sau

y=7.9830x-1.9335

y = ^.3334x-0.4502

8 -0.6 -0.4 -0.2

-+

0.4 0.6 0.8

Hang so Hammet

</div>
(61)<div class='page_container' data-page=61>

Hai dd thi hinh 2.6, 2.7 cd hinh dang tuong tu \di dd thi 2.3 va 2.4 md ta
anh hudng cua nhdm the lan moment ludng cue. Dieu nay chung td rang nhdm tha'
anh hudng da'n hinh hgc cua phan tu khong dang ka nhu ddi vdi mdment ludng
cue.

Riang trudng hgp nhdm the p-OH ddi vdi ca hai dang phan tu A4X va B2X
va trudng hgp nhdm the 0CH3 ddi vdi phan tu B2X, cac gia tri khdng tuan theo
trat tu. Dieu nay cho thay su bien ddi dang ka cua ca'u tnic hinh hgc phan tu
A40H, B20H va B2OCH3 ddi vdi cac phan tu khae cung kiau.

2.5.3 Anh hudng cua nhdm the lan dien tfch cua nguvan tu Oxy :

Dian tfch cua nguyan tu O xy rd rang chiu anh hudng cua hieu ung nhdm tha'. Bang
2.9 dudi day tdng ket cac ket qua tfnh dugc vdi hai kieu phan tu A4X va B2X

Bang 2.9 : Dien tfch dinh cu tran nguyan tu oxy thude phan tu A4X va B2X

X
NH2 
OH
0CH3 
CH3 
H
F
Hang so
Hamet
-0.66
-0.37

-0.268
-0.17
0
0.062

qO tren phan tu kieu
A4X
-0.32387
-0.32096
-0.32152
-0.31961
-0.31918
-0.31768

qO tren phan tu kieu B2X

</div>
(62)<div class='page_container' data-page=62>

d day : GTTB la gia tri trung binh dien tfch ciia mdi kiau phan tu.

Su phu thugc cua q O vao ban chat cua cac nhdm the ciia 2 kiau phan tu A4X va

B2X duoc bieu dian tran hinh :

c

Hang so Hammet q O A4X

qO B2X

Hinh 2.8: Su phu thugc cua dien tfch dinh cu tran nguyan tu O vao nhdm tha

Dua vao ket qua thu dugc budc dau ta cd the nit ra mot sd nhan xet sau :

-f- Ddi vdi ca hai kia'u phan tu, su tang ciia gia tri hang sd Hammet ( tii cac
nhdm the day electron chuyen sang cac nhdm the cang hiit electron ), gia tri dien
tfch dinh cu tran nguyan tu O tang ( nghTa la gia tri tuyet ddi ciia dien tfch giam ).
Diau nay cd tha coi la phu hgp vi sU canh tranh electron ciia nhdm the va nhdm
CO. Ket qua nay mot lan nua cho thay anh hirong ciia nhdm the lan nhdm CO
trong mach thugc kieu phan tii B2X manh hon kieu A4X.

</div>
(63)<div class='page_container' data-page=63>

+ Cac nhdm the anh hudng manh hon lan dien tfch dinh cu ciia nguyan tu
Oxy trong phan tu B2X neu so vdi phan tu kiau A4X , cung edn tha hien d gia tri
ha sd gdc cua hai dudng thang hdi qui tga :

tga,,, =0.0092 
tga,,, =0.0\7\

tga,,, 0.0171 
tga,,, 0.0092 ^2

Nhu vay, anh hudng ciia nhdm the len nguyen tu O kiau B2X manh ga'p ddi
lan nguyan td O trong phan tu kieu A4X. Diau cd the giai thfch dua vao ca'u tao
cua phan tu A4X va B2X. Cdng thuc cua phan tu B2X la
XC6H4-CO-C2H2-C4H3S, phan tu A4X : XC6H4-C2H2-CO-XC6H4-CO-C2H2-C4H3S, do nhdm CO ndi true tia'p vdi
nhan phenyl cd nhdm the para, do do se chiu anh hirdng cua nhdm the Idn hon. 
Cung dua vao sir phat trien deu dan trong hinh sd [2.8] , chiing ta cd tha tian
doan mdt anh hudng rat yeu ciia vdng thiophene lan phan tu .

2,5A Anh hudng ciia nhdm the len neuvan tu S va di vdng thiophen:

Dien tfch dinh cu tran nguyan tu S dugc tdng ket dudi bang sau :

Bang 2.10 : Dien tfch dinh cu tran nguyan tu S thugc phan tu A4X va B2X

Phan tu
NH2

OH
0CH3

CHS
H
F
CI
Br

Hamet
-0.66
-0.37
-0.27
-0.17
0.00
0.06
0.23
0.23

qSA4x

0.672661

0.675140
0.673980

0.675499 1
0.674000

0.679743 1

0.679746

1

. 1 
0.680694 :

Q SB2X

</div>
(64)<div class='page_container' data-page=64>

CN

N02

0.66

0.78 0.684538 0.582092

0.689573 1 0.588070

Dd thi duoc bieu dian

C/3

e

Urn

X

c

•5'

X

s

tooo

0.65000O

-0^.630000--0^.640000

-0.590000

0 560000^

y = 0.0089X + 0 . 5 7 7 9

80 - 0 . 6 0 - 0 . 4 0 -0.20 0.00 0.20 0.40
H dng su H a m e t

0.60 q SA4X 
q SB2X

Hinh 2.9 : Su phu thugc ciia dien tfch dinh cu tren nguyan tu S \'a(^ nhdm the

Dua vao ket qua tfnh toan va dd thi tran hinh 2.9 ta cd cac nhan xet nhu sau :

+ Dien tfch dinh cu tran nguyan tii S trong di vdng thiophen tang theo kha 
nang hiit electron ciia nhdm the.

+ Dua vao gia he so gdc cua dudng thang hdi qui thi anh hudng cua nhdm
the la tuong ddi nhd. Anh hudng nay la tuong tu nhau ddi vdi ca hai kiau phan tu

tga,,, 0.0113

A4X va B2X. ( - 1 )
iga,,, 0.0089

Diau nay phu hgp vdi cac ket qua lap luan ciia phan khao sat anh hudng cua
nhdm the len nguyan tu O.

2.5.4 Anh hudne ciia nhdm the den dao done ciia phan tu.

</div>
(65)<div class='page_container' data-page=65>

Phan tu B2 cd gdc xoan giiia hai H ciia nhdm vin\ 1 trong phan tu B2X la 2 oC ,

trong khi dd phan tu A4X la ddng phang. Chiing toi quan tam den mot sd dao
dong sau day :

Bang 2.11 : Gia tri v thuc nghiem [31], [32] va ly thuyet cho cac dao dong C=0,
CH=CH j,,,3 C-H,go^i ^,j phang' C=C cua phan tu A4X

X
NH2
OH
OCH3

cm

H
F
CI
Br
CN
N02
.S.STD,,
vv=.,
TN
1690
1685
1663
1687
1620
1681
1689
1673
1660
1670

LT
1689
1681
1671
1658
1628
1682
1696
1692
1661
1709
0.696%

^'rH=< H irir,.

TN
990
988
990
989
985
987
991
989
984
LT
977
981
993
978

988
992
981
981
988
978

^ ("-H H'-.-'.i ni.li rh.in- ^ t =C

TN
805
810
818
810
830
821
814
831
LT
817
818
808
812
819
818
818
818
819
818
0.762% 0.965%

TN
1610
1580
1601
1605
1611
1608
1612
1605
LT
1584
1585
1583
1583
1582
1581
1580
1594
1581
1578
1.359%

Bang 2.12 : Gia tri \' thuc nghiam[31]. [32] va ly thuyet cho cac dao ddng C=0,
CH=CH (,,,, C-H,g,,aimaiphang^ C=C cua phan tu B2X

X
NH2
OH
OCH.3
CH.^

H
F
\'c=u
TN
1685
1682
1670
1661
1635
LT
168544
1686
1672
1666
1627
1681 1689
\'rH=rH lr.,n.
TN
981
979
885
981
984
977
LT
987
975
987
975
977

C - H :,••• .11 m.il rh.irii'

</div>
(66)<div class='page_container' data-page=66>

CI
Br
CN
N02

SSTDTP

1632

1673 
1649 
1637

1624 
1677 
1659 
1623 
0.384%

980
970

980

976

967

812
810
966

1.585%

978 821

811

810

1609

1605 
812

812

0339%

1595

1603 
1598 
1600 
1594 
0 304%

Chii thfch : S S T D J B : nghTa la gia tri lay trung binh ciia cac sai sd tuong ddi giua

gia tri tfnh ly thuyet va ket qua thuc nghiem theo [31]. [32]

Tir cac ket qua thu dugc chiing tdi cd cac ket luan sau :

Phuong phap tfnh gan diing ly thuyet theo phuong phap PM3 kha tin cay
trong khoang tii 98 - 99.59^. Tat ca cac dao ddng dang chii y deu xuat hien.

Dua vao cac ket qua thdng ka, phuong phap tfnh loan va phan tfch dao
ddng theo AMI kha chfnh xac ddi vdi cac dao dong C = 0 , CH=CH,,„„. C-H „j.oaini.i
phang . C=C, tuy nhien ddi vdi v^^-^^ ^'^^^ g'^'» ^H '>' thuyet nho h(yn cac gia Iri thuc 
nghiem .

</div>
(67)<div class='page_container' data-page=67>

CHUONG III: KET LUAN CHUNG

•

Cac thdng sd lugng tu dugc tfnh toan nhd cac phuong phap ban thuc nghiem
trong phan mam Hyperchem cho cac dan xuat the p-phenyl thugc day a,(5 xeton
khong no chua di bong thiophen bao gdm : nang lugng lien kei. nang lugiig texm
phan, nhiet hinh thanh, dien tfch dinh cu. mo ment ludng cue. tan sd dao dong va
cau triic hinh hgc d trang thai hoi da cho phep chiing toi riit ra dugc cac nhan xet
sau :

1. Vdi ddi tugng khao sat nhu tran, cac phuong phap ban thuc nghiem td ra
phii hgp nhat la :

-f De tfnh toan nang lugng lian ket, nang lugng toan phan, nhiet hinh
thanh nan sir dung phuong phap ZINDO/S

+ Di tdi im hoa hinh hgc va phan tfch xac dinh tan sd dao dong, 
quay, xac dinh dien tfch dinh cu nan sir dung phuofng phap AM 1

-I- Di tfnh toan gia tri momen lufrng cue ncn su dung phuong phap 
PM3.

2. Trong tam cau dang gia thiet ciia hcrp chai nghien cuu, thi hai kieu chai
cd dang A4 va B2 la ban hon ca, dac biet phan tu B2 khdng ddng phang.

3. Ccic nhdm the anh hudng den nang lugng lien ket. nang lugng toan phan
va nhiet hinh thanh, phan tii B2NO2 va phan tu A4 NO^ la cac phan tu ben hon ca.

4. Ddi vdi ca hai kiau phan tu, moment ludng cue (D) tang theo gia tri tuyet
ddi cua hang sd Hamet. Nhdm the day electron anh hirdng manh hon nhdm the
hiit electron . Nhdm the OH cd anh hirdng khdng nam trong qui luat nay

5. Cac nhdm the nhin chung cd anh hirong rai ft den cau tri'ic hnih hgc cua
nhan phenyl va nhan thiophenon loai trii cac nhdm the OH.

6. Dien tich dinh cu Wen nguyen tu O ( mang dau -) tang theo chicu tang 
ciia gia tri hfing sd Hamet ( chicu tang tfnh day electron ).

</div>
(68)<div class='page_container' data-page=68>

8. Cac gia tri vi tfnh toan tan sd dao dong tuong ddi chfnh xac, cac dao 
dong C = 0 va C=C cho thay sir lien hgp electron pi trong loan he thdng.

</div>
(69)<div class='page_container' data-page=69>

TAI LIEU THAM KHAO

Tieng Viet.

1 Huynh Tan Dung - Cam nang tra cmi EXCEL 4.0 & 5.0 Ham va Macro. 
NXB D6ng Xai 1995 .Tr. 125,140,170.

2 Dang Van Giap - Phan tfch du Heu khoa hoc b^ng chuong trinh
MS-EXCEL. NXB Giao Due. 1997.Tr. 45.70.84.

3 Nguydn Dmh Hud, Nguydn Due Chuy, Su gan diing cac hat doc Lip, Tliuyet
luong tir ve nguyen tCr va phan tu. Tap L NXB Giao Due 1986 . Tr.80. 95.
4 Le Due Ngoc - Giao Trinh Xu ly va ke hoach hoa thuc nghiem .

1998.Tr.20,45,70.

5 TrSn Quoc Son - Giao trinh co .so ly thuyet hoa hoc hOru co. NXB Giao Due
1989. Tr. 40,55.

6 Phan Tong Son. Tran Quoc Son, Dang Nhu Tai, Hop chii't tap chue, Ca sd 
hoa hoc hiju co, NXB Dai hoc va THCN, Tap I Tr. 153157. Tap II Tr. 400
-420.

7 Dang Nhu Tai - Hoa hoe lap the. NXB Giao Due 1997. Tr. 14,20,125.
8 Nguyen Minh Thao- Hoa hoc cac hop chat di vong. NXB Giao Due

1982.Tr. 12,34,45,200.

9 Lam Ngoc Thiem- Giao trinh Co so hoa hoe lugng tu. Tapl. NXB KH va
KT 1999.

10 Dao Dinh Tliire - Cau tao nguyen tu va lien ket hoa hoc , NXB GD 1985. Tr.
100,234,270.

</div>
(70)<div class='page_container' data-page=70>

Tieng La tinh

12 P. W, Atkins; R. S. Friedman, Molecular Quantum Mechanics, 3rd Ed., 
Oxford, New York, 1997, p. 276.

13 T. Clark, A Handbook of Computational Chemistr}-. New York:
Wiley-Interscience (1985).

14 M.J.S Dewar Theo MO theory of organic chemistry . Me Graw Hill Book
Co. 1969. P. 25-74,369-472.

15 M.J.S Dewar, Thiel W. Ground states of molecules. 38 The MNDO
Method Applications and parameters. J. Am.Chem. Soc. 1977 P. 4899 - 4907

16 M.J.S Dewar , Thiel W. Ground states of molecules. 39 MNDO results for
molecules containt H,C,N,0. 1977 P.4907 -4917

17 M.J.S Dewar, Zocbbisch E.G, Healy E.F. AMI a new general purpose
quantum mechanical molecular model. J. Am. Chem. Soc 1985 P 3902 - P 3909

18 D. M. Etter . Enginering problem solving with Matlab. Prentice Hall
International, Inc.

19 James B. Foresman, A.E leen Frisch. Exploring Chemistry with Electronic
Structure Methods. 1993 Gaussian Inc.

20 J. B. Foresman and a. Frisch, Exploring Chemistry with Electronic Structure

Methods, Gaussian, Pittsburgh, 1996, p 115.

21 J. B. Foresman and /E. Frisch, Exploring Chemistry with Electronic

Structure Methods. Gaussian. Pittsburgh. 1995-96, p. 118.

22 W.J. Hehre, L. Radom, P.v.R. Schleyer, J.A. Pople, Ab Initio Molecular
Orbital Theory. New York: Wiley-Interscience (1986).

23 Hypechem release 2 for windows 1992. Autodeck Inc.

24 J. H. Krieger, '^Computational Chemistry Impact'', C&E News, 1997, May , 
p 30.; E. K. Wilson, "Computers Customize Combinatorial Libraries", C&E News,

1998, April 27, p 31.

</div>
(71)<div class='page_container' data-page=71>

27 J.J.P Stewart. Optimazation of parameters for semiempherical methods I. J.
Comput. Chem. 1989 P 221 -264.

28 A.Szabo., The antisymmetry or Pauli E.xelusion principle, Modem Quantum
Chemistry, Macmilan Publ. Co., Inc.

29 At. Szabo., The Hartree - Fock Apprx. Modem Quantum Chemistr>',
Macmilan Pub. Co., Inc, P 100 - 120.

30 A. Szabo and N.S. Ostlund, Modem Quantum Chemistry Introduction to
Advanced Electronic Structure Theory. New York: McGraw-Hill Publishing Co.
(1989).

31 S.V Tsykerman. V.D. Orlov, I.S. Rozum. nV.F. Lavrusin. j.khim Geterosikl.
Xoedin 1969 P. 6,974.

</div>
(72)<div class='page_container' data-page=72></div>
(73)<div class='page_container' data-page=73>

Phu luc 1 - Ket qua tinh trong phan chon phurnig phap.

/perChem log start-- Sat Oct 02 15:18:14 1999.

ngle Point. SemiEmpirical. molecule = C:\HYPER\BINH\CH0NPH-1\HIN\AM1A1 HIN
siDO

MERCIES AND GRADIENT
)tal Energy

)tal Energy
nding Energy

Diated Atomic Energy
ectronic Energy
Dre-Core Interaction
3at of Formation

radient =
pole (Debyes) x y

)int-Chg. -0.258 1.997
(Hybrid -0.284 3.222
I Hybrid 0.000 0.000
jm -0.543 5.220

= -80752.1751428 (kcal/mol)
= -128.684213033 (a.u.)

= -8349.5281562 (kcal/mol)

= -72402.6469866 (kcal/mol)
= -341570.2321314 (kcal/mol)

= 260818.0569886 (kcal/mol)
= -5480.9791562 (kcal/mol)

88.4359271 (kcal/mol/Ang)
z Total
0.000 2.014
0.000 3.235
0.000 0.000
0.000 5.248

ngpoint CNDO cho Mau A l toi uu hoa hinh hoc bang A M I
^perChem log stop - Sat Oct 02 15:19:20 1999.

^perChem log start ~ Sat Oct 02 15:19:48 1999.

ngle Point, SemiEmpirical, molecule = C:\HYPER\BINH\CH0NPH-'1\HIN\AM1A1 HIN
DO

sJERGIES AND GRADIENT
ital Energy

•tai Energy
nding Energy

)lated Atomic Energy
ectronic Energy
)re-Core Interaction

jat of Formation
adient

pole (Debyes) x
•int-Chg. -0.978
Hybrid -0.133
Hybrid 0.000
m -1.111
y
3.529
2.673
0.000
6.202

ih bang Indo A l toi uu hoa bang A M I

perChem log stop - Sat Oct 02 15:20:45 1999

= -78299.6309830 (kcal/mol)
= -124.775913169 (a.u.)

= -8111.9146391 (kcal/mol)
= -70187.7163440 (kcal/mol)
= -339117.6879717 (kcal/mol)

= 260818.0569886 (kcal/mol)
= -5243.3656391 (kcal/mol)

94.8270934 (kcal/mol/Ang)
z Total

0.000 3.662
0.000 2.677
0.000 0.000
0.000 6.301

perChem log start - Sat Oct 02 15:22
igle Point, SemiEmpirical, molecule =
ND03

lERGIES AND GRADIENT

tai Energy =
tai Energy =
iding Energy =
lated Atomic Energy =
sctronic Energy =

-re-Core Interaction =

:28 1999

C: \HYPER\BINH\CH0NPH-1\HIN\AM1 A1 .Hlh

</div>
(74)<div class='page_container' data-page=74>

=*oint-Chg.
sp Hybrid
Dd Hybrid
Bum
-0.598
-0.226
0.000

-0.825
3.562
2.560
0.000
6.122
0
0.
0.
0.

Tinh bang MIND03 A l toi uu bang A M I

Zonvl Limit :0.0001, Iteration : 50 , U

HyperChem log stop - Sat Oct 02 15:23:

HF
37
3.612
2.57
0
6,178
1999

Single Point, SemiEmpirical, molecule = C:\HYPER\B1NH\CH0NPH-1\H1N\AM1A1 HIN
MNDO

Convergence limit = 0.0001000 Iteration limit = 50
ENERGIES AND GRADIENT

Total Energy
Total Energy
Binding Energy

Isolated Atomic Energy
Electronic Energy
Core-Core Interaction
Heat of Formation
Gradient

Dipole (Debyes) x
Point-Chg. -0.008
sp Hybrid -0.287
pd Hybrid 0.000
Sum -0.296
y
1.314
2.409
0.000
3.723

Tinh bang Mndo A l toi uu hoa bang A M I
Conv. Limit : 0.0001/ Iteration : 50/UHF

HyperChem log stop - Sat Oct 02 15:24:57 1999.

-54235.2477497 (kcal/mol)
-86.427643131 (a.u.)
= -2821.8090557 (kcal/mol)

= -51413.4386940 (kcal/mol)
= -290278.9656419 (kcal/mol)

= 236043.7178922 (kcal/mol)
46.7399443 (kcal/mol)
10.4999197 (kcal/mol/Ang)
z Total
0.000 1.314
0.000 2.426
0.000 0.000
0.000 3.735

HyperChem log start - Sat Oct 02 15:26:36 1999.

Single Point, SemiEmpirical. molecule = C:\HYPER\B1NH\CH0NPH-1\H1N\AM1A1.H1N 
PM3

ENERGIES AND GRADIENT
Total Energy

Total Energy
Binding Energy

Isolated Atomic Energy
Electronic Energy
Core-Core Interaction
Heat of Formation
Gradient

Dipole (Debyes) x

Point-Chg. -0.096
sp Hybrid -0.254
pd Hybrid 0.000

1.367
2.253
0.000
3.620

= -50083,1210231 (kcal/mol)

= -79.810940123 (a.u.)
= -2819.2325471 (kcal/mol)

= -47263.8884760 (kcal/mol)
= -282143.9023070 (kcal/mol)

= 232060.7812838 (kcal/mol)
49.3164529 (kcal/mol)
11.1492538 (kcal/mol/Ang)
z Total
0.000 1.371
0.000 2.267
0.000 0.000
0.000 3.637
Sum -0.350

Tinh bang PM3 A1 toi uu hoa bang A M I

Sonv. limit : 0.0001/ Iteration : 50/ UHF

HyperChem log stop - Sat Oct 02 1 5:27:07 1999
HyperChem log start - Sat Oct 02 15:27:31 1999,

</div>
(75)<div class='page_container' data-page=75>

Total Energy =

-Binding Energy =
solated Atomic Energy

Electronic Energy =
^ore-Core Interaction

Heat of Formation =
3radient =
Dipole (Debyes) x y

=^oint-Chg. -0.616 3.422
Bp Hybrid -0.182 2.673
3d Hybrid 0.000 0.000
Sum -0.799 6.095
Tinh bang ZINDOI A l toi uu h
Conv. limit : 0.0001/ Iteration :
HyperChem log stop - Sat Oct

•118.139692132 (a.u.)
-8325.2810394 (kcal/mol)
= -65809.9752249 (kcal/mol)
-334953.3132529 (kcal/mol)
= 260818.0569886 (kcal/mol)

'• -5456.7320394 (kcal/mol)

57.9304681 (kcal/mol/Ang)
z Total
0.000 3.477
0.000 2.679
0.000 0.000
0.000 6.147
oa bang A M I
50/UHF

02 15:27:59 1999.

HyperChem log start - Sat Oct
Single Point, SemiEmpirical, m
ZINDOS

ENERGIES AND GRADIENT
Total Energy = •
Total Energy = •

Binding Energy =
Isolated Atomic Energy

Electronic Energy =
Core-Core Interaction

Heat of Formation

-Gradient =
Dipole (Debyes) x y

Point-Chg. -0.197 4.583
sp Hybrid -0.270 2.662
pd Hybrid 0.000 0.000
Sum -0.467 7.244
Tinh bang Z1ND03A1 toi uu h
Conv. limit : 0.0001/ Iteration :
HyperChem log stop - Sat Oct

02 15:28:28 1999.

olecule = C:\HYPER\BINH\CH0NPH-1\H1N\AM1A1.HIN,

-63067,8842271 (kcal/mol)
-100.503064284 (a.u.)

-10837.4823961 (kcal/mol)
= -52230,4018310 (kcal/mol)
-261849.8073997 (kcal/mol)

= 198781.9231726 (kcal/mol) 
-- -7968.9333961 (kcal/mol)

194.0158609 (kcal/mol/Ang)
z Total
0.000 4.587
0.000 2.675
0.000 0.000

0.000 7.259

oa bang A M I
50/UHF

02 15:29:00 1999.

HyperChem log start - Sat Oct 02 15:25:17 1999.

Single Point, SemiEmpirical, molecule = C:\HYPER\B1NH\CH0NPH-1\H1N\AM1A1.HIN
A M I

Convergence limit = 0.0001000 Iteration limit = 50
ENERGIES AND GRADIENT

Total Energy
Total Energy
Binding Energy

Isolated Atomic Energy
Electronic Energy
Core-Core Interaction
Heat of Formation
Gradient

Dipole (Debyes) x
Point-Chg. 0.141

y
0.681

= -53384.1918050 (kcal/mol)

= -85.071426233 (a.u.)

= -2825.2554050 (kcal/mol)
= -50558.9364000 (kcal/mol)
= -288856.7067461 (kcal/mol)

= 235472.5149412 (kcal/mol)
= 43,2935950 (kcal/mol)

3.1427011 (kcal/mol/Ang)
z Total

</div>
(76)<div class='page_container' data-page=76>

"inh bang A M I A1 toi uu hoa bang A M I
^onv. limit : 0.0001/ Iteration : 50/ UHF

</div>
(77)<div class='page_container' data-page=77>

Phu luc 2 : Ket qua tim dong phan ben nhat
( Tinh theo phuomg phap ZINDO/S )

perChem log start - Fri Oct 08 21:06:24 1999.

igle Point, SemiEmpirical, molecule = C:\HYPER\B1NH\KHA0SA-1\HINASE-1\A1.H1N.
sJDOS

K^

"otal Energy = -63068.19175 (kcal/mol)
'otal Energy = -100.5035543 (a.u.)

binding Energy = -10837.78992 (kcal/mol)
solated Atomic Energy = -52230.40183 (kcal/mol)
Electronic Energy = -261860.7231 (kcal/mol)
:ore-Core Interaction = 198792.5313 (kcal/mol)
Heat of Formation = -7969.240918 (kcal/mol)
Sradient = 194.0056505 (kcal/mol/Ang)
rperChem log start - Fri Oct 08 21:05:28 1999.

ngle Point. SemiEmpirical, molecule = C:\HYPER\B1NH\KHA0SA-1\HINASE-1\A2.HIN.
NDOS

\2

Total Energy = -63070.63006 (kcal/mo!)
Total Energy = -100.50744 (a.u.)
Binding Energy = -10840.22823 (kcal/mol)
solated Atomic Energy = -52230.40183 (kcal/mol)
Electronic Energy = -262861.4645 (kcal/mol)
:ore-Core Interaction = 199790.8344 (kcal/mol)
Heat of Formation = -7971.679233 (kcal/mol)
Bradient = 193.5923871 (kcal/mol/Ang)
(perChem log start - Fri Oct 08 21:05:56 1999.

ngle Point, SemiEmpirical, molecule = C:\HYPER\B1NH\KHA0SA-1\HINASE-1\A3.HIN.
NDOS

Total Energy = -63075.54422 (kcal/mol)
Total Energy = -100.515271 (a.u.)

Binding Energy = -10845.14238 (kcal/mol)
solated Atomic Energy = -52230.40183 (kcal/mol)
Electronic Energy = -260742.1092 (kcal/mol)
:ore-Core Interaction = 197666.565 (kcal/mol)
Heat of Formation = -7976.593384 (kcal/mol)
Gradient = 193.7233195 (kcal/mol/Ang)
rperChem log start - Fri Oct 08 21:06:54 1999.

ngle Point, SemiEmpirical, molecule = C:\HYPER\BINH\KHA0SA-1\HINASE-1\A4.HIN
MDOS

</div>
(78)<div class='page_container' data-page=78>

lyperChem log start - Fri Oct 08 21:07:44 1999.

ingle Point. SemiEmpirical. molecule = C:\HYPER\BINH\KHA0SA-1\HINBSE-1\B1.H1N.
INDOS

Total Energy = -63082.7231 (kcal/mol)
Total Energy = -100.5267111 (a.u.)
Binding Energy = -10852.32127 (kcal/mol)
Isolated Atomic Energy = -52230.40183 (kcal/mol)
Electronic Energy = -263487.1555 (kcal/mol)
Core-Core Interaction = 200404.4324 (kcal/mol)
Heat of Formation = -7983.772269 (kcal/mol)
Gradient = 195.0616983 (kcal/mol/Ang)
HyperChem log s t a r t - Fri Oct 08 21:08:10 1999.

>ingle Point, SemiEmpirical, molecule = C:\HYPER\B1NH\KHA0SA-1\H1NBSE-1\B2.H1N.
:iNDOS

Total Energy = -63083.54074 (kcal/mol)
Total Energy = -100,528014 (a.u.)
Binding Energy = -10853,1389 (kcal/mol)
Isolated Atomic Energy = -52230.40183 (kcal/mol)
Electronic Energy = -264283.8696 (kcal/mol)
Core-Core Interaction = 201200.3288 (kcal/mol)
Heat of Formation = -7984.589904 (kcal/mol)
Gradient = 194.6170005 (kcal/mol/Ang)
HyperChem log s t a r t - Fri Oct 08 21:08:46 1999.

Single Point, SemiEmpirical, molecule = C:\HYPER\BINH\KHA0SA-1\H1NBSE-1\B3.H1N.
71NDOS

Total Energy = -63068.99127 (kcal/mol)
Total Energy = -100.5048284 (a.u.)
Binding Energy = -10838.58944 (kcal/mol)
Isolated Atomic Energy = -52230.40183 (kcal/mol)
Electronic Energy = -260719.586 (kcal/mol)
Core-Core Interaction = 197650.5947 (kcal/mol)
Heat of Formation = -7970.040436 (kcal/mol)
Gradient = 194.5130767 (kcal/mol/Ang)
HyperChem log s t a r t - Fri Oct 08 21:09:26 1999.

Single Point. SemiEmpirical, molecule = C:\HYPER\BlNH\KHAOSA-1\HlNBSE-1\B4.HlN
ZINDOS

Total Energy = -63072.70736 (kcal/mol)
Total Energy = -100.5107503 (a.u.)
Binding Energy = -10842,30553 (kcal/mol)
Isolated Atomic Energy = -52230,40183 (kcal/mol)
Electronic Energy = -260798.3554 (kcal/mol)
Core-Core Interaction = 197725,648 (kcal/mol)
Heat of Formation = -7973,756527 (kcal/mol)

</div>
(79)<div class='page_container' data-page=79>

Phu luc 3 : Ket qua khao sat phat trien mach

perChem log start - Thu Oct 21 18:00:46 1999.

rational Analysis, SemiEmpirical, molecule = C:\HYPER\BINH\D0NGPH-2 DONGPH-1 \KHA0SA-2vHINFIL-1\

•NZEN.HIN. ZINDOS
iERGIES AND GRADIENT

tai Energy =
tai Energy =
iding Energy =
)lated Atomic Energy =

sctronic Energy =
•re-Core Interaction =
lat of Formation =

adient =
-23615.1 (kcal/mol)
-37.6323 (a.u.)
-4860.71 (kcal/mol)
-18754.4 (kcal/mol)
-66644.6 (kcal/mol)
43029.53 (kcal/mol)
-3522.76 (kcal/mol)
167.6247 (kcal/mol/Ang)

'perChem log start - Thu Oct 21 18:04:26 1999.

rational Analysis, SemiEmpirical, molecule = C,\HYPER\BINH\DONGPH-2\DONGPH-1\KHAOSA-2\HINFIL'1\

IHYDE.HIN. ZINDOS
JERGIES AND GRADIENT

tai Energy =
tai Energy =
iding Energy =
)lated Atomic Energy =

ectronic Energy =
ire-Core Interaction =
sat of Formation =

adient =
-28105,6 (kcal/mol)
-44.7883 (a.u.)

-5924.35 (kcal/mol)
-22181.3 (kcal/mol)
-87731.2 (kcal/mol)
59625.59 (kcal/mol)
-4311.31 (kcal/mol)
170.3181 (kcal/mol/Ang)

'perChem log start - Fri Dec 24 18:41:42 1999.

national Analysis. SemiEmpirical. molecule = C:\HYPER\BINH\PHATTR-1\H1NF1L-1\BETHYL.H1N
^DOS

JERGIES AND GRADIENT

tai Energy =
tai Energy =
iding Energy =
)lated Atomic Energy =

ectronic Energy =
•re-Core Interaction =
!at of Formation =

adient =
-31460.7 (kcal/mol)
-50.1349 (a.u.)
-6454.9 (kcal/mol)
-25005.8 (kcal/mol)
-102452 (kcal/mol)
70991.65 (kcal/mol)

-4670.96 (kcal/mol)
166.9375 (kcal/mol/Ang)

perChem log start - Thu Oct 28 18:47:44 1999.

igle Point. SemiEmpirical, molecule = C:\HYPER\BlNH\DONGPH-2\DONGPH-1vKHAOSA-2\HINFIL-1\
HYDE.HIN. ZINDOS

lERGIES AND GRADIENT

tai Energy =
tai Energy =
iding Energy =

lated Atomic Energy =

-42427,6 (kcal/mol)
-67.6113 (a.u.)
-7557.58 (kcal/mol)

</div>
(80)<div class='page_container' data-page=80>

Gradient = 202.2016 (kcal/mol/Ang)

HyperChem log start - Fri Dec 24 18:03:37 1999.

Single Point. SemiEmpincal, molecule = C:\HYPER\BINH\PHATTR-1\HINFIL-1\2BZET HIN
ZINDOS

ENERGIES AND GRADIENT

Total Energy = -65177.1 (kcal/mol)

Total Energy = -103.864 (a.u.)
Binding Energy = -12155 (kcal/mol)
Isolated Atomic Energy = -53022 (kcal/mol)
Electronic Energy = -283311 (kcal/mol)
Core-Core Interaction = 218134 (kcal/mol)
Heat of Formation = -8906.9 (kcal/mol)
Gradient = 183.6989 (kcal/mol/Ang)

HyperChem log s t a r t - Fri Oct 08 21:06:54 1999,

Single Point, SemiEmpirical, molecule = C:\HYPER\BINH\KHA0SA-1\HINASE-1V\4 HIN
ZINDOS

ENERGIES AND GRADIENT

Total Energy = -63075,7976986 (kcal/mol) 
Total Energy = -100.515674952 (a.u.) 
Binding Energy = -10845,3958676 (kcal/mol)
Isolated Atomic Energy = -52230,4018310 (kcal/mol)
Electronic Energy = -260473 6816683 (kcal/mol)
Core-Core Interaction = 197397,8839697 (kcal/mol) 
Heat of Formation = -7976,8468676 (kcal/mol)
Gradient = 193.9819894 (kcal/mol/Ang)

HyperChem log start - Fri Oct 08 21:08:10 1999.

Single Point, SemiEmpirical, molecule = C:\HYPER\BlNH\KHAOSA-1\HlNBSE-1\B2,HIN
ZINDOS

ENERGIES AND GRADIENT

Total Energy = -63083.5407350 (kcal/mol)
Total Energy = -100.528014019 (a.u.)
Binding Energy = -10853.1389040 (kcal/mol)
Isolated Atomic Energy = -52230.4018310 (kcal/mol)
Electronic Energy = -264283.8695688 (kcal/mol)
Sore-Core Interaction = 201200.3288338 (kcal/mol)
Heat of Formation = -7984,5899040 (kcal/mol)
Sradient = 194.6170005 (kcal/mol/Ang)

fCliao sat momen liJOngx - phat triOii mach cue bang PM3
rlypeiChcm lou st^irl - S;U Jun 17 03:16:37 2000.

Miiglc Point, ScmiCmpirical, molecnie = C:\IIYPi:R\BLNaT\PM3\FrMACH\BENZEN.HIN.
^M3

3ipoIe (Debyes) x
^oint-Chg.

;p Hybriti
)d Hybrid

0.000
0.000

0.000

y

0.000

0.000
0.000

</div>
(81)<div class='page_container' data-page=81>

HyperChem log start - Sat Jun 17 03:17:00 2000.

Single Point, SemiEmpirical, molecule = C:\HYPER\BINKvPM3\PTMACH\TOLUEN.HIN.
PM3

Dipole (Debyes) x y z Total
Point-Chg. 0.233 -0.152 0.007 0.278
sp Hybrid -0.019 -0.002 0.008 0.020
pd Hybrid 0.000 0.000 0.000 0.000
Sum 0.214 -0.154 0.015 0.264
HyperChem log slop - Sat Jun 17 03:17:06 2000.
HyperChem log starl - Sat Jun 17 03:17:27 2000.

Single Point, SemiEmpirical, molecule = C:\HYPLR\0INH\PM3\FrMy\Cl-KSTYREN.HIN.
PM3

Dipole (Debyes) x y z Toial
Point-Chg. -0.011 -0.004 0.000 0.012
sp Hybrid 0.005 0.000 0.000 0.006
pd Hybrid 0.000 0.000 0.000 0.000
Sum -0.006 -0.003 0.000 0.007
HyperChem log slop - Sal Jun 17 03:17:31 2000.

HyperChem log start - Sat Jun 17 03:17:54 2000.

Single Point, SemiEmpirical, molecule = C:\HYPER\BINH\PM3\PTMACH\C1NAMHYD.H1N
PM3

ipole (Debyes) x y z Total
Point-Chg. -2.520 -0,033 0,010 2,521
sp Hybrid -0.401 -0.150 0.003 0.428
pd Hybrid 0.000 0.000 0.000 0.000
Sum -2.921 -0.183 0.013 2,927
HyperChem log stop - Sat Jun 17 03:17:58 2000.
HyperChem log start - Sat Jun 17 03:18:16 2000.

Single Point. SemiEmpirical, molecule = C:\HYPER\B1NH\PM3\PTMACH\2BZET,HIN. 
PM3

Dipole (Debyes) x y z Total
Point-Chg. -2.098 -0.859 0.007 2.267
sp Hybrid -0.359 -0.301 0.003 0.468
pd Hybrid 0.000 0.000 0.000 0.000
Sum -2.457 -1.160 0.010 2.717
HyperChem log stop - Sat Jun 17 03:18:21 2000.
HyperChem log start - Tue Aug 01 13:43:17 2000.

Single Point, SemiEmpincal, molecule = C;\BlNH\HYPER\BlNH\DPMOIV\4\KHAOSA-lvHINFIL-1\A4.HIN.

PM3

Dipole (Debyes) x y z Total
Point-Chg. -0.811 -0.167 0.017 0.828
sp Hybrid -2.068 -1.039 -0.021 2.315
pd Hybrid 0.000 0.000 0.000 0.000
Sum -2.879 -1.206 -0.004 3.122
HyperChem log stop -- Tue Aug 01 13:43:27 2000.

HyperChem log start - Tue Aug 01 13:56:53 2000.

</div>
(82)<div class='page_container' data-page=82></div>
(83)<div class='page_container' data-page=83>

hu luc 4 : Ket qua tinh n^ng lurmg toan phan , n^ng luomg lien ket va nhiet hinh
thanh.

perChem log start - Sat Oct 09 15:41:30 1999.

)le Point, SemiEmpirical, molecule = C: HYPER\BlNH\D0NGPH-2VD0NGPH-rXHA0SA-1\HINFIL-1\

NH2.HIN. ZINDOS

ERGIES AND GRADIENT

[al Energy = -69097.0563438 (kcal/mol)
tai Energy = -110.110969801 (a.u.)
iding Energy = -11827.6721960 (kcal/mol)
lated Atomic Energy = -57269.3841478 (kcal/mol)
jctronic Energy = -293529.7906749 (kcal/mol)
re-Core Interaction = 224432.7343311 (kcal/mol)
at of Formation = -8794.0211960 (kcal/mol)
adient = 204.5045171 (kcal/mol/Ang)
perChem log s t a r t - Mon Oct 11 20:24:57 1999.

gle Point, SemiEmpirical, molecule = C.\HYPER\BINH\D0NGPH-2\D0NGPH-1 KHAOSA-VHINFIL-1

tOH.HIN. ZINDOS

lERGIES AND GRADIENT

tai Energy = -70737.5308823 (kcal/mol)

tai Energy = -112.725180187 (a.u.)
iding Energy = -11467.5042078 (kcal/mol)
ilated Atomic Energy = -59270.0266744 (kcal/mol)
jctronic Energy = -295400.1296680 (kcal/mol)
ire-Core Interaction = 224662.5987857 (kcal/mol)
lat of Formation = -8539.3962078 (kcal/mol)
adient = 218,2560478 (kcal/mol/Ang)
perChem log start - Mon Oct 11 20:09:37 1999.

gte Point, SemiEmpirical, molecule = C: HYPER\BINH\D0NGPH-2^.D0NGPH-1 KHAOSA-nHINFIL-l

^0CH3.HIN. ZINDOS
iERGIES AND GRADIENT

tai Energy = -75207.7810928 (kcal/mol)
tai Energy = -119.848835115 (a.u.)
iding Energy = -12510.8478473 (kcal/mol)
)lated Atomic Energy = -62696.9332454 (kcal/mol)
jctronic Energy = -328402.3011821 (kcal/mol)
ire-Core Interaction = 253194.5200894 (kcal/mol)

3{ of Formation = -9307.6458473 (kcal/mol)

adient = 207.3917267 (kcal/mol/Ang)
perChem log start - Sat Oct 09 14:32:39 1999.

gle Point, SemiEmpincal, molecule = C HYPER\BINH\D0NGPH^2 DONGPH-1 KHAOSA^I HINFIL^1^4CH3,HIN.

MDOS

JERGIES AND GRADIENT

</div>
(84)<div class='page_container' data-page=84>

ore-Core Interaction = 224035.2450167 (kcal/mol)
eat of Formation = -8767.7002418 (kcal/mol)
radient = 192.5054310 (kcal/mol/Ang)
yperChem log start - Fri Oct 08 21:06:54 1999.

ngle Point, SemiEmpincal, molecule = C:vHYPER£INH\KHA0SA-l\HlNASE-'l\A4.HIN.

INDOS

NERGIES AND GRADIENT

3tal Energy = -63075.7976986 (kcal/mol)
otal Energy = -100.515674952 (a.u.)
inding Energy = -10845.3958676 (kcal/mol)
olated Atomic Energy = -52230.4018310 (kcal/mol)
lectronic Energy = -260473.6816683 (kcal/mol)
ore-Core Interaction = 197397.8839697 (kcal/mol)
eat of Formation = -7976.8468676 (kcal/mol)

radient = 193.9819894 (kcal/mol,/Ang)
yperChem log start - Sat Oct 09 15:55:35 1999.

ngle Point, SemiEmpincal, molecule = C;\HYPER\BINH\DONGPH-2\DONGPH-1\KHAOSA-1\HINFlL-1\A4F.HIN.

INDOS

NERGIES AND GRADIENT

otal Energy = -73053.4370838 (kcal/mol)
otal Energy = -116.415737952 (a.u.)
inding Energy = -11062.3768343 (kcal/mol)
,olated Atomic Energy = -61991.0602495 (kcal/mol)
lectronic Energy = -297387.4675153 (kcal/mol)
ore-Core Interaction = 224334.0304314 (kcal/mol)
eat of Formation = -8227.0398343 (kcal/mol)
iradient = 213.1218181 (kcal/mol/Ang)

yperChem log start - Sat Oct 09 14:53:16 1999.

ngle Point, SemiEmpirical. molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-1\KHAOSA-1\HINFIL-1\A4CN.HIN.

INDOS

NERGIES AND GRADIENT

Otal Energy = -71204.6592144 (kcal/mol)
otal Energy = -113.469581706 (a.u.)

inding Energy = -11713.0751356 (kcal/mol)
iolated Atomic Energy = -59491.5840789 (kcal/mol)

lectronic Energy = -302420.3059842 (kcal/mol) 
ore-Core Interaction = 231215.6467698 (kcal/mol)
eat of Formation = -8612.7381356 (kcal/mol)
,radient = 220.9253602 (kcal/mol/Ang)

yperChem tog start - Mon Oct 11 19:55:22 1999.

ngle Point, SemiEmpincal. molecule = C \HYPER\BINH\D0NGPH-2\D0NGPH-1 XHAOSA-1'.HINFlL-rA4N02.HlN.

INDOS

NERGIES AND GRADIENT

</div>
(85)<div class='page_container' data-page=85>

perChem log start - Mon Oct 11 20:46:25 1999.

gle Point, SemiEmpincal, molecule = C ,HYPER^BlNH:DONGPH-2.DONGPH-2-,KHAOSA-1\HINFlL'1\B2NH2 HIN

^JDOS

JERGIES AND GRADIENT

tai Energy = -69109.3927849 (kcal/mol)
ital Energy = -110.130628779 (a.u.)
nding Energy = -11840.0086370 (kcal/mol)
)lated Atomic Energy = -57269.3841478 (kcal/mol)
ectronic Energy = -298566.8600231 (kcal/mol)
)re-Core Interaction = 229457.4672382 (kcal/mol)
jat of Formation = -8806,3576370 (kcal/mol)
-adient = 204.4665465 (kcal/mol/Ang)
/perChem log start - Tue Oct 12 12:33:17 1999.

igle Point, SemiEmpincal, molecule = C .HYPER\BlNH\DONGPH-2^-.DONGPH-2\KHAOSA-1\HINFIL-VB20H,HIN.

NDOS

vJERGlES AND GRADIENT

)tal Energy = -70747.2788513 (kcal/mol) 
)tal Energy = -112.740714255 (a.u.)

nding Energy = -11477.2521769 (kcal/mol)
olated Atomic Energy = -59270.0266744 (kcal/mol)

ectronic Energy = -300424.7704293 (kcal/mol)
ore-Core Interaction = 229677.4915780 (kcal/mol)
eat of Formation = -8549.1441769 (kcal/mol)
radient = 218.7410794 (kcal/mol/Ang)
yperChem log s t a r t - Mon Oct 11 21:52:49 1999.

ngle Point, SemiEmpincal. molecule = C,\HYPER\BINH\D0NGPH-2\D0NGPH-2\KHA0SA-1\HINF1L-1\B20CH3 HIN,

INDOS

NERGIES AND GRADIENT

otal Energy = -75216.8835327 (kcal/mol)
otal Energy = -119.863340487 (a.u.)
inding Energy = -12519.9502873 (kcal/mol)
olated Atomic Energy = -62696.9332454 (kcal/mol)
lectronic Energy = -335076.6423913 (kcal/mol)
ore-Core Interaction = 259859.7588585 (kcal/mol)
eat of Formation - -9316.7482873 (kcal/mol)
.radient = 207.7897725 (kcal/mol/Ang) 
yperChem log start - Sat Oct 09 16:21:21 1999.

ngle Point, SemiEmpirical. molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-2XHAOSA-l\HINFIL-1\B2CH3.HIN.

INDOS

NERGIES AND GRADIENT

otal Energy = -54544.9858310 (kcal/mol)
otal Energy = -102.856928525 (a.u.)
inding Energy = -8887.6774290 (kcal/mol)
;olated Atomic Energy = -55657.3084020 (kcal/mol)

</div>
(86)<div class='page_container' data-page=86>

NDOS

^ERGIE AND GRADIENT

'tai Energy = -63083.5 (kcal/moO
•tai Energy = -100,528 (a.u.)
nding Energy = -10853.1 (kcal/mol)

)lated Atomic Energy = -52230.4 (kcal/mol)
ectronic Energy = -264284 (kcal/mol)

)re-Core Interactio = 201200.3 (kcal/mol)

^at of Formation = -7984.59 (kcal/mol) 
•adient = 194.617 (kcal/mol/Ang)

yperChem log start - Mon Oct 11 20:37:33 1999.

igle Point, SemiEmpirical, molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-2\KHAOSA-1VHINFIL-nB2F HIN

NDOS

sJERGlES AND GRADIENT

)tal Energy = -73062.5577021 (kcal/mol)
)tal Energy = -116.430272292 (a.u.)
nding Energy = -11071.4974526 (kcal/mol)
Diated Atomic Energy = -61991.0602495 (kcal/mol)
ectronic Energy = -302375.0030237 (kcal/mol)
)re-Core Interaction = 229312.4453216 (kcal/mol)
?at of Formation = -8236.1604526 (kcal/mol)
•adient = 213.7345538 (kcal/mol/Ang)
yperChem log start - Sat Oct 09 17:02:45 1999.

igle Point, SemiEmpincal, molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-2\KHAOSA-1\HINFIL-1\B2CN.HIN.

NDOS

NJERGIES AND GRADIENT

»tal Energy = -68063.1499150 (kcal/mol)
Ital Energy = -108.463367926 (a.u.)
nding Energy = '-8571.5658361 (kcal/mol)
Diated Atomic Energy = -59491.5840789 (kcal/mol)
ectronic Energy = -304504.9169549 (kcal/mol)
)re-Core Interaction = 236441.7670400 (kcal/mol)
jat of Formation = -5471.2288361 (kcal/mol)
•adient = 280.4586653 (kcal/mol/Ang)
yperChem log s t a r t - Mon Oct 11 21:14:19 1999.

gle Point, SemiEmpincal, molecule = C HYPER\BINH\DONGPH'-2\DONGPH-2.KHACSA-1\HINFIL-l \B2N02.HIN.

NDOS

sIERGIES AND GRADIENT

»tal Energy = -83166.3708180 (kcal/mol)
ital Energy = -132.531401917 (a.u.)
nding Energy = -12420.0903033 (kcal/mol)
)lated Atomic Energy = -70746.2805147 (kcal/mol)
ectronic Energy = -364723.9966114 (kcal/mol)
)re-Core Interaction = 281557.6257934 (kcal/mol) 
;at of Formation = -9371.5253033 (kcal/mol)

</div>
(87)<div class='page_container' data-page=87>

Phu luc 5 : Tong ket phan tich dao dong bang AMI

perChem log start - Sat Nov 27 15:47:25 1999.

rational Analysis, SemiEmpirical, molecule = C;vHYPER\BINH\D0NGPH~2VD0NGPH-1VKHA0SA-1\HINFIL-1 V\4NH2 HIN.

«1

ormal Mode Frequency 817.19
28 Intensity 38.48743

ormal Mode Frequency 976.55
39 Intensity 0.15759

ormat Mode Frequency 1584.15
57 Intensity 89.27677

ormal Mode Frequency 1689.03
59 Intensity 2.85091

rperChem log start - Sat Nov 27 18:14:19 1999.

rational Analysis, SemiEmpirical, molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-1\KHAOSA-1\HINFIL-1W40H.HIN.

ormal Mode Frequency 817.92
27 Intensity 35.31769

ormal Mode Frequency 980.77
36 Intensity 0.35854

ormal Mode Frequency 1585.09
55 Intensity 64.59732

ormal Mode Frequency 1681.75
57 Intensity 118.85686

perChem log start - Sat Nov 27 16:52:06 1999.

rationalAnalysis. SemiEmpirical. molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-1\KHAOSA-l\HINFIL-1\A40CH3.HIN.

HI

ormal Mode Frequency 807.77
29 Intensity 35.73719

ormal Mode Frequency 992.54
39 Intensity 2.35540

ormal Mode Frequency 1582.52
63 Intensity 84.79372

ormal Mode Frequency 1671.40
64 Intensity 118.26834

perChem log start - Fri Nov 26 12:47:01 1999.

rational Analysis. SemiEmpirical, molecule = C:\HYPER\BINH\DONGPH-2.DONGPH-1XHAOSA~r^iNFlL-1\A4CH3.HIN.

/I1

ormal Mode Frequency 812.17
27 Intensity 14.57574

ormal Mode Frequency 977.66
37 Intensity 13.09646

ormal Mode Frequency 1582.59
60 Intensity 81.30569

</div>
(88)<div class='page_container' data-page=88>

lormal Mode Frequency 819.34
25 Intensity 15.76425

lormal Mode Frequency 988.44
34 Intensity 4.20526

lormal Mode Frequency 1581.88

53 Intensity 86.92366

Jormal Mode Frequency 1628.23

54 Intensity 15.34308

yperChem log start - Sat Nov 27 14:44:16 1999.

brational Analysis, SemiEmpincal. molecule = C;\HYPER\B1NH\D0NGPH-2\D0NGPH-1\KHA0SA-1\H1NFIL-1\A4F HIN.

Jormal Mode Frequency 817.91
26 Intensity 34.06317

sJormal Mode Frequency 991.10
36 Intensity 2.95766

slormal Mode Frequency 1581.53
54 Intensity 78.13848

^Jormal Mode Frequency 1682 16
56 Intensity 49.61940

lyperChem log s t a r t - Sat Nov 27 12:31:21 1999.

ibrational Analysis, SemiEmpincal, molecule = C \HYPER\B1NH\D0NGPH-2\D0NGPH-1\KHA0SA-1\HINFIL-1V\4CL HIN.

.Ml

Slormal Mode Frequency 817.93
27 Intensity 38.56583

sJormal Mode Frequency 980.84
37 Intensity 5.39909

vJormal Mode Frequency 1579.81
54 Intensity 69.78465

sJormal Mode Frequency 1695.55
57 Intensity 17.00077

lyperChem log start - Tue Nov 23 18:34:34 1999.

ibrationalAnalysis. SemiEmpincal, molecule = C:\HYPER\B1NH\D0NGPH-2\D0NGPH-1\KHA0SA-1\HINFIL-1\A4BR.HIN.

.Ml

Slormal Mode Frequency 817.76
27 Intensity 37.11484

sjormal Mode Frequency 981.10
37 Intensity 5.77002

Slormal Mode Frequency 1594.15
55 Intensity 12.93028

Normal Mode Frequency 1692.35

57 Intensity 0.00951

lyperChem log start - Sat Nov 27 13:47:15 1999.

'ibrational Analysis. SemiEmpincal, molecule = C .HYPER\B1NHOONGPH-2.DGNGPH-.1 KHAOSA^I >HirJFlL-VA4CN.HIN

^M1

Slormal Mode Frequency 819,05
28 Intensity 32,80869

</div>
(89)<div class='page_container' data-page=89>

57 Intensity 12 60590

HyperChem log s t a r t - Sat Nov 27 16:21:29 1999.

Vibrational Analysis, SemiEmpincal, molecule = C:\HYPER BlNH\DONGPH-2»DONGPH-rvKHAOSA-1\HiNFlL-1W4N02 HIN

\M1

Normal Mode Frequency 817.90
30 Intensity 29.69402

Normal Mode Frequency 977.53
38 Intensity 11.75253

Normal Mode Frequency 1578.51
58 Intensity 119.91637

Normal Mode Frequency 1708.76
60 Intensity 109.48035

HyperChem log start - Sat Dec 04 15:02:27 1999.

/ibrational Analysis, SemiEmpincal, molecule = C:\HYPER\BINH\DONGPH-2\DONGPH-3\KHAOSA-l\HINFIL-1\B2NH2 HIN.

!\M1

Normal Mode Frequency 809.72
27 Intensity 31.75664

Normal Mode Frequency 987.31
37 Intensity 1.99030

Normal Mode Frequency 1605.45
57 Intensity 19.10003

Normal Mode Frequency 1685.44
58 Intensity 16.72604

HyperChem log start - Mon Dec 06 19:42:06 1999.

/ibrational Analysis. SemiEmpirical, molecule = C:\HYPER\B1NH\D0NGPH-2\D0NGPH-3\KHA0SA-1\HINF1L~-1\B20H,HIN.

^M1

Normal Mode Frequency 808.04
26 Intensity 21.21315

Normal Mode Frequency 975.32
35 Intensity 7.60701

Normal Mode Frequency 1604.12
56 Intensity 17.70499

Normal Mode Frequency 1685.89
57 Intensity 35.02803

HyperChem log start - Sat Dec 04 16:47:08 1999.

/Ibrational Analysis, SemiEmpincal, molecule = C \HYPER .BINH'DONGPH-2 D 0 N G P H - 3 K H A 0 S A - 1 ;HiNFiL-1 ,B20CH3.H1N. \

\M1 1

Normal Mode Frequency 810.50 \ 
29 Intensity 33.41365

Normal Mode Frequency 986.98
38 Intensity 2.48416

Normal Mode Frequency 1599.09
63 Intensity 20.13363

Normal Mode Frequency 1672.51
64 Intensity 38.48303

HyperChem log start - Sat Dec 04 10:31:33 1999.

</div>
(90)<div class='page_container' data-page=90>

Normal Mode Frequency 975.53

35 Intensity 9.22989

Normal Mode Frequency 1603.73
60 Intensity 15.12296

Normal Mode Frequency 1666.15
61 Intensity 6.03716

HyperChem log start - Sat Dec 04 09:47:40 1999.

Vibrational Analysis, SemiEmpincal, molecule = C .HYPER\BINH\DONGPH-2\DONGPH-2\KHAOSA-l\HINFlL-1\B2 HIN

A M I

Normal Mode Frequency 810.26
24 Intensity 34.07725

Normal Mode Frequency 977.50
33 Intensity 16.75135

Normal Mode Frequency 1599.74
53 Intensity 14.37782

Normal Mode Frequency 1627.26
54 Intensity 14.46574

HyperChem log start - Sat Dec 04 14:39:40 1999.

Vibrational Analysis, SemiEmpincal. molecule = C ,HYPER BINH\D0NGPH-2>D0NGPH-3\KHA0SA-1\HINF1L-1\B2F HIN.

AMI

Normal Mode Frequency 811.49
26 Intensity 27.03259

Normal Mode Frequency 975.70
34 Intensity 7.51800

Normal Mode Frequency 1603.93
54 Intensity 17.74155

Normal Mode Frequency 1689.43
55 Intensity 14.47440

HyperChem log start - Sat Dec 04 11:10:05 1999.

Vibrational Analysis, SemiEmpincal, molecule = C.\HYPER\BINH\D0NGPH-2O0NGPH-3\KHA0SA-1\HINFlL-1\B2CL.HIN,

AMI

Normal Mode Frequency 810.99
26 Intensity 33.87395

Normal Mode Frequency 975.96
35 Intensity 9.13659

Normal Mode Frequency 1602.59
54 Intensity 19.42497

Normal Mode Frequency 1623.88
55 Intensity 3.89110

HyperChem log start - Sat Dec 04 10:07:47 1999.

Vibrational Analysis, SemiEmpincal, molecule = C .HYPER.BINH D0NGPH^2 D0NGPH^3.KHA0SA^1\HINFIL-1 B2BR HIN.

AM1

Normal Mode Frequency 810.44
28 Intensity 34.66134

Normal Mode Frequency 966.61
35 Intensity 12.88526

</div>
(91)<div class='page_container' data-page=91>

yperChem log start - Sat Dec 04 11:36:39 1999.

brational Analysis, SemiEmpincal. molecule = C.vHYPER\BiNH\DONGPH-2\DONGPH-3\KHAOSA-1VHiNFlL-1\B2CN.HIN.

Jormal Mode Frequency 812.01
28 Intensity 34.65174

Jormal Mode Frequency 966.18
35 Intensity 7.73619

Jormal Mode Frequency 1600.28
56 Intensity 16.16817

sJormal Mode Frequency 1658.81
57 Intensity 7.90497

lyperChem log start - Sat Dec 04 15:42:34 1999.

ibrational Analysis, SemiEmpincal, molecule = C:\HYPER\BINH\D0NGPH-2\D0NGPH-3\KHA0SA-1\HINFIL-1\B2N02H1N

.Ml

^Jormal Mode Frequency 812.36
29 Intensity 32.82346

Normal Mode Frequency 977.83
38 Intensity 10.62059

Normal Mode Frequency 1594.00
58 Intensity 18.11538

</div>
(92)<div class='page_container' data-page=92>

hu luc 6 : Ket qua tfnh toan moment lirong cue bang phuong phap PM3

yperChem log start - Tue Aug 01 13:52:53 2000.

ngle Point. SemiEmpincal, molecule = C: .BINH\HYPER\BirjH\DPIV10l A 4 X H A 0 S A - 1 \HINFIL-1\A4NH2 HIN

ipole (Debyes) x y z Total
ointChg. 2.194 0.761 0.028 2.322 
-) Hybrid -2.094 -1.026 -0.977 2.528
j Hybrid 0.000 0.000 0.000 0.000
um -4.288 -0.265 -0.949 4.400
yperChem log stop - Tue Aug 01 13:53:03 2000.
yperChem log start - Tue Aug 01 13:55:51 2000.

ngle Point, SemiEmpincal. molecule = C:\BINH\HYPER\BINH\DPM0IV\4\KHA0SA-1\H1NFIL~1W40H HIN

M3
ipole (De
oint-Chg.
3 Hybrid
j Hybrid
um
byes) X
-0.520
-1.846
0.000
-2.366
y
0.246
-0.411
0.000
-0.166
z
-0,076
-0.065
0.000
-0.141
Total
0.580
1.892
0,000
2.376
yperChem log stop - Tue Aug 01 13:55:59 2000,

yperChem log start - Tue Aug 01 13:54:58 2000.

ngle Point, SemiEmpirical, molecule = C:\BINH^HYPER\BINH\DPIV10I\A4'KHA0SA-1\HINFIL-1 V\40CH3 HIN

ipole (Debyes) x y z Total
oint-Chg. -0.879 0.809 -0.098 1.198
) Hybrid -1.876 -0.782 -0.069 2.034
j Hybrid 0.000 0,000 0,000 0,000
um -2.755 0,026 -0.168 2.760
yperChem log stop - Tue Aug 01 13:55:10 2000.
yperChem log start - Tue Aug 01 13:45:34 2000.

igle Point, SemiEmpirical, molecule = C \BINH\HYPER\BINH\DPMOIV\4\KHAOSA-l\HINFIL-1V\4CH3.HIN.

ole (Debyes) x y z Total
oint-Chg. -1.190 0.052 0.036 1.192
) Hybrid -2.063 -1.055 -0.032 2.318
J Hybrid 0.000 0.000 0.000 0.000
j m -3.254 -1.003 0.004 3.405
/perChem log stop - Tue Aug 01 13:45:41 2000,
/perChem log start - Tue Aug 01 13:43:17 2000.

igle Point, SemiEmpirical. molecule = C.\BINH\HYPER\BINH\DPM0[V\4KHA0SA-1 hilNFIL-1 ^4,HIN

VI3

</div>
(93)<div class='page_container' data-page=93>

/perChem log stop - Tue Aug 01 13:43:27 2000.
/perChem log start - Tue Aug 01 13:48:03 2000.

igle Point. SemiEmpirical, molecule = C BlNH.HYPER>BirJH^DPM01V\4\KHA0SA-1\HINFlL-1 A4F HIN,

pole (Debyes) x y z Total
Dint-Chg. 0.644 -1.045 0.017 1.228
) Hybrid -2.022 -1.057 -0.022 2.282
i Hybrid 0.000 0.000 0.000 0.000
j m -1.378 -2.102 -0.005 2.514
yperChem log stop - Tue Aug 01 13:52:06 2000.
)erChem log start - Tue Aug 01 13:46:24 2000.

ngle Point, SemiEmpirical, molecule = C:\BINH\HYPER\BINH\DPMOIW4\KHAOSA-1\HINFIL-rA4CL.HIN.

ipole (Debyes) x y z Total
oint-Chg. -0.400 -0.466 0.019 0.614
) Hybnd -1.617 -1.277 -0.023 2.061
j Hybrid 0.000 0.000 0.000 0.000
um -2.017 -1.743 -0.004 2.666
yperChem log stop - Tue Aug 01 13:46:30 2000.
yperChem log start -- Tue Aug 01 13:44:10 2000.

ngle Point, SemiEmpincal, molecule = C,\BINH\HYPER\BINH\DPMOIVi.4\KHAOSA-1\HINFlL-1\A4BR HIN

ipole (Debyes) x y z Total
oint-Chg. 0.113 -0,781 0.018 0.790
0 Hybrid -1.988 -1.069 -0.022 2,258
d Hybrid 0.000 0.000 0.000 0.000
um -1.875 -1.850 -0.004 2.635
yperChem log stop - Tue Aug 01 13:44:17 2000.
yperChem log start - Tue Aug 01 13:47:16 2000.

ngle Point. SemiEmpirical. molecule = C:\BINH\HYPER\BINH\DPM0IV\4\KHA0SA-1\HINFIL-1V^4CN.H1N.

'ipole (Debyes) x y z Total
oint-Chg. 1.919 -1.869 0.017 2.679
p Hybrid -1.345 -1.414 -0.023 1.952
d Hybrid 0.000 0.000 0.000 0.000
um 0.574 -3.283 -0.005 3.333
lyperChem log stop - Tue Aug 01 13:47:25 2000.
lyperChem log start - Tue Aug 01 14:05:03 2000.

•ngle Point. SemiEmpincal, molecule = C.\BINH\HYPER\BINH.DPM01.B2,KHA0SA-1 h l N F l L - l B2NH2 HIN

</div>
(94)<div class='page_container' data-page=94>

pole (Debyes) x
>int-Chg. -3.182
Hybrid 1.140
Hybrid 0.000
im -2.041
y

-1.057
0.031
0.000
-1.026
z Total
1.088 3.525
-1.028 1.536
0.000 0.000
0.060 2.286
'perChem log stop - Tue Aug 01 14:08:02 2000.
(perChem log start - Tue Aug 01 14:06:54 2000.

igle Point, SemiEmpirical, molecule = C BINH.HYPER\BINH\DPM0I\B2\KHA0SA-1\HINFIL-1 B20CH3 HIN

;13

pole (Debyes) x y z Total
)int-Chg. -4.305 -1.595 0.472 4.615 '

Hybrid 0.990 -0.898 -1.370 1.914
: Hybrid 0.000 0.000 0.000 0.000
jm -3.315 -2.492 -0.898 4.243
YperChem log stop - Tue Aug 01 14:07:02 2000.
yperChem log start - Tue Aug 01 14:00:28 2000.

igle Point. SemiEmpirical, molecule = C.\ElNH\HYPERB!NH\DPMOi\B2\KHAOSA-1\HINFIL-1\B2CH3.HIN.

^3
pole (De
)lnt-Chg.

Hybrid
1 Hybrid
j m
byes) X
-3.854
1.019
0.000
-2.836
y
-1.151
-0.597
0.000
-1.748
z
0.867
-1.358
0.000
-0.491
Total
4.115
1.799
0.000
3.367
/perChem log stop - Tue Aug 01 14:00:36 2000.
/perChem log start - Tue Aug 01 13:56:53 2000

igle Point,:
yi3
pole (De
)int-Chg,

Hybrid
; Hybrid
i m
SemiEmpirical,
ibyes) X
-3.481
1.014
0.000
-2.467
molecule =
y
-1.362
-0.553
0.000
-1.916
C\BINH\HYPER\BIN
z Total
0.887 3.842
-1.354 1.780
0.000 0.000
-0.467 3.158
/perChem. log stop - Tue Aug 01 13:57:00 2000.
/perChem log start -- Tue Aug 01 14:03:49 2000.

igle Point, SemiEmpirical, molecule = C:\BlNH\HYPER\BINH\DPMOI\B2\KHAOSA-1\HINFlL-rB2F.HIN.

pole (Debyes) x y z Total
)int-Chg. -2.066 -2.166 0.980 3.150

Hybrid 1.075 -0.571 -1.340 1.811
Hybrid 0.000 0 000 0.000 0,000
im -0.991 -2.737 -0 360 2 933
'perChem log stop - Tue Aug 01 14:03:55 2000.
'perChem log start - Tue Aug 01 14:01:20 2000.

gle Point, SemiEmpincal, molecule = C BlNH^HYPERB;NH>,DPM0rB2,KHA0SA-l HINFIL-1 B2CL HIN

/13

</div>
(95)<div class='page_container' data-page=95>

-1.650 -2.399 -0.393 2.938
:hem log stop - Tue Aug 01 14:01:27 2000.
:hem log start - Tue Aug 01 13:57:50 2000.

Dint, SemiEmpirical, molecule = C:\BINH\HYPERVBINH\DPM01\B2XHAOSA-1vHINFlL-1B2BR HIN

(Debyes) x y z Total
:hg. -2.296 -2.070 0.973 3.241
.rid 1.159 -0.605 -1.339 1.871
)rid 0.000 0.000 0.000 0.000
-1.137 -2.675 -0.365 2.930
: h e m log stop - Tue Aug 01 13:57:56 2000.
: h e m log start - Tue Aug 01 14:02:35 2000.

oint, SemiEmpincal, molecule = C:\B1NH\HYPERB1NH\DPM0I\B2\KHA0SA-1\HINF1L-1\B2CN.H1N.

(Debyes) x y z Total
: h g . -0.947 -2.826 1.080 3,170
)rid 1.774 -0,888 -1.287 2,365

x i d 0,000 0.000 0.000 0.000
0,827 -3.714 -0.207 3.810
2hem log stop - Tue Aug 01 14:02:42 2000.
Chem log start - Tue Aug 01 14:06:01 2000.

oint, SemiEmpincal, molecule = C \BINH\HYPER\BINH\DPM01\B2KHA0SA-1 ,HINF1L-1\B2N02 HIN

</div>
(96)<div class='page_container' data-page=96>

Phu luc 7: The tinh dien va mat do dien tich t6ng 
i A4 : I M tinh dien ( Electrostatic Potential )

LT A4 : Mat d6 didn tfch t^ng ( Total charge Density )

</div>
(97)<div class='page_container' data-page=97>

A4 : Tha tinh didn ( Electrostatic Potential)

X

\

B2: MAl-d6 didn lich tdng ( Total charge.Density )

..^'^

</div>
(98)<div class='page_container' data-page=98>

Phuluc 8 : Pho IR

IR Spectrum A4

§ §

§ § ^ J § ,

So song cm-1

§ §

IR spectrum B2

g § §

§- § §

8 §

</div>


<a href=''> ni.li rh.in</a>

Nghiên cứu quan hệ giữa tính chất và cấu trúc dãy Anpha, Beta-Xeton không no chứa dị vòng Thiophen bằng phương pháp tính gần đúng lượng tử

<b>BO GIAO DUG VA DAO TAO </b>

<b>DAI HOC QUOC GIA H A N O I </b>

<b>TRirdNG DAI HOC KHOA HOC lUNHIEN </b>

<b>Le Thai Binh </b>

NGHIEN COU QUAN HE

CHAT VA CAU TRUC DAY

a,p - XETON KHONG NO CHLfA Dl VONG THIOPHEN BANG

PHl/ONG

TINH GAN

Ll/ONG TLf

LUAN AN THAC SI KHOA HOC HOA HOC

Chuyen nganh : Hoa Ly

Ma so: 1-04-04

Ngudi huong dan khoa hoc :

PGS.TS Lam Ngoc Thi6m

<b>MUG LUC </b>

<b>MOOAU </b>

CHirONG 1 -TONG QUAN

<i>^ = -^t^y'^-V^t K-TI.^'Z,r:^.l^e^Z,Z,r-l.j:e^r-; (1.05) </i>

<i>!H = - - 4 M ; v=-xi;.^z,.;>x.v-/ (1.06) </i>

<i>// = / / ' X Z e'r-; (1.08) </i>

<i><b>II'%; = I I 7 =11^. </b></i>

^ = Z^"' + ZZ-^""^-ZX^'.^> (1-15)

<i>K^„ = J K ( ' k ( ' ) f V^.OkO>/r,^r^ (1.17) </i>

<i><b>k'A </b></i>

I ^ / J ^ , - V J = 0 v6rii:l,2...M (1.21)

^ > Z O ' (1.23)

^. = ^. ^ 1(2^.. - ^.J

<i>•^... = i\I.^'jM </i>

<i>JI^JM) </i>

<b>!",;>. (2) </b>

<b><sub>Z^',/>.(2) </sub></b>

<b>^.^ = W </b>

<b>Z «.>,(!), </b>

Z^^'V.O)

<i>K<p,i'~) </i>

<b>Z^'./>X2) </b>

<i>(/vu|H= JK0K(2)-^, OM (2) (^^^) n.32) </i>

TOM LAI

<b>o </b>

<b>f ^ </b>

<b>5 ^ </b>

<b>5. ^; </b>

<b>i| </b>

<i><b>9 </b></i>

<b>Q </b>

<b>n </b>

<b>o </b>

<b>O </b>

c=c-c

<b>o </b>

o ^

<b>Q </b>

c-c=c

o ^

AH

kcal/mol

769

507

578

612

Nang lugmg 6n dinh

kcal/mol

37.9

16

16

11

<i><b>^^.r^'^^ </b></i>

c=c-c

<b>o </b>

<b>o </b>

c-c=c ^

<b>^6 ^ </b>

c=c-c

<b>o </b>

s"

CHLONG 2: PHAN THLC NGHIEM VA BIEN LUAN

KET QUA

<i><b>f-</b></i>