27 CSLT - Hoa - Hoc TS LE MINH DUC PDF

Bai giang
C s
ly thuyet hoa hoc
__&&&__
TS. Le Minh c
Bo mon Cong nghe hoa hoc-khoa hoc vat lieu
Trng ai hoc Bach Khoa a Nang
http://hhud.tvu.edu.vn
1. CHNG 1: C S HO LNG T ............................................... 1

1.1. Gii thiu chung 1
1.2. M hnh nguyn t Rutherford 1
1.3. Hm sng, phung trnh sng Schrdinger 2
1.3.1. Hm sng ton phn, i xng, phn i xng 3
1.3.2. Nguyn l chng cht cc trng thi 4
1.4. Ton t trong c hc lng t 4
1.4.1. Cc nh ngha v ton t 4
1.4.2. Biu din mt i lng vt l 6
1.4.3. Phng trnh ton t tng qut 6
2. CHNG 2: CU TRC ELECTRON NGUYN T......................... 8
2.1. Nguyn t H v ion ging H 8
2.1.1. Phng trnh Schrdinger 8
2.1.2. Orbital nguyn t (AO) 8
2.1.3. Spin v nng lng electron 9
2.2. Nguyn t nhiu electron 11
2.2.1. M hnh h cc electron c lp 11
2.2.2. Hm sng ton phn 12
2.2.3. Nguyn tc nghin cu h nhiu electron 14
3. CHNG 3: CU TO PHN T - LIN KT HO HC ............ 17
3.1. Kho st lin kt CHT trn c s lng t 17
3.1.1. Hn ch ca cc thuyt c in v lin kt ho hc v cu to
phn t 17
3.1.2. Kho st lin kt ho hc v cu to phn t trn c s Ho
lng t 18
3.2. Phng php lin kt ho tr 18
3.2.1. Gii phng trnh Schrdinger 18
3.2.1.1. Phng trnh 18
3.2.1.2. Gii phng trnh 19

3.2.2. Bn cht lin kt cng ho tr 22
3.3. Phng php orbital phn t (MO) 22
3.3.1. Phng php t hp tuyn tnh cc AO (Linear Combination of
Atomic Orbital - LCAO) 23
3.3.2. Phng php MO cho hai nguyn t ging nhau 25
3.3.2.1. Bi ton H 2+ 25
3.3.2.2. iu kin cc AO t hp to thnh MO 28
3.3.3. Phng php MO cho hai nguyn t khc nhau 29
3.3.4. Phng php MO phn t c nhiu nguyn t 30
3.3.5. Phng php Hckel 33
3.3.5.1. Bi ton 33
3.3.5.2. Mt electron , bc lin kt v ch s ho tr t do 33
4. CHNG 4: I XNG ..................................................................... 35
4.1. Khi nim 35
4.2. Cc php i xng c bn 35
4.2.1. Php quay quanh trc vi gc quay 2/n 35
4.2.2. Php phn chiu qua mt phng 36
4.2.3. Php phn chiu quay Sn 37
4.2.4. Php chuyn o i 37
5. CHNG 5: M PHNG CU TRC PHN T ............................ 38
5.1. Gii thiu phn mm Gaussian 98 38
5.2. Nhp lnh v chy chng trnh 38
5.3. Phn tch kt qu 39
Ti liu tham kho

1. Nguyn Vn Xuyn, Ho l - Cu to phn t v lin kt ho hc,
NXB KHKT H ni, 2005.
2. o nh Thc, Cu to nguyn t v lin kt ho hc, NXB Gio dc,
2005, tp 1 & 2.
3. Lm Ngc Thim, Bi tp Ho lng t c s, NXB KHKT, 2003
3. Arvi Rauk, Orbital interaction theory of organic chemistry, 2001
J.Wiley.
4. Donald D. Fitts, Principles of quantum mechanics as applied to
Chemistry and Chemical Physics, 2002.
5. Iran. Levin, Quantum Chemistry, 2000.
1. CHNG 1: C S HO LNG T
1.1. Gii thiu chung
Vt l hc c in l phn vt l khng k n thuyt tng i ca Einstein
v thuyt lng t ca Planck, n da trn hai h thng l thuyt c bn l c
hc ca Newton v thuyt in t ca Maxwell.
Vt l hc c in cho kt qu ph hp vi thc nghim i vi cc hin
tng vt l m ngi ta bit n cui th k XIX, n l h thng l thuyt
hon chnh v cht ch trong phm vi ng dng cu n.
u th k XX, c nhng hin tng vt l khng th gii thch c bng
cc l thuyt ca vt l hc c in nh: hiu ng quang in, hiu ng compton,
quang ph nguyn t, tnh bn ca nguyn t, bc x ca vt en. . .
C hc lng t (quantum mechanics) ra i nghin cu vi ht, xy
dng trn c s cc tnh cht v c im chuyn ng ca vi ht. C hc lng
t l l thuyt ca nhng h nguyn t v ht nhn, chng c kch thc c 10-13
n 10-15m. Nhng ht c kch thc nh vy c gi l nhng ht vi m.
Ho lng t (quantum chemistry) l vic p dng c hc lng t gii
quyt cc bi ton hc hc. Ho hc lng t nh hng su rng n tt c
cc lnh vc ca ho hc. Cc nh ho l p dng ho lng t tnh ton
cc thng s nhit ng hc (nhit dung, entropy) ca cht kh, gii thch cc
tnh cht ca phn t nh: di lin kt, gc lin kt, momen lng cc, sai
khc nng lng gia cc dng ng phn, xc nh cc trng thi chuyn tip
(transition states).
Ngy nay, c rt nhiu phn mm tnh ton trn c s lng t. Cc phn
mm ny c s dng rng ri, khng dnh ring cho cc nh ho lng t.
1.2. M hnh nguyn t Rutherford

Khi electron chuyn ng xung quanh ht nhn trn mt qu o bn knh
r, s c cn bng gia sc ht tnh in v lc ly tm
__________________________________________________________________________________________
Bi ging C s L thuyt Ho hc
TS. L Minh c
2
mv 2 ( Ze)e
= 2 ;
r
r
v2 =
1
2
ng nng ca electron c tnh: T = mv 2 =
Ze 2
mr
Ze 2
2.r
Lc ht tnh in gia ht nhn v in t c tnh: F =
Ze2
r2
Gi A l cng cn thit di chuyn electron t khong cch r n v tn,

ta c
Ze 2
Ze 2
1
1
A = 2 dr = Ze 2 2 dr = Ze 2
=
rr
r
r r
r r
Ngc li, khi electron chuyn ng t n khong cch r i vi ht

nhn, electron s thc hin c mt cng A, nng lng gim i mt lng
ng bng nh th. Gi U l th nng ca electron v cng, U r l th nng ca
electron qu o c bn knh r.
Ur = U A = U
Ze 2
r
Quy c U = 0 th th nng ca electron trn qu o vi bn knh r s l:

Ze 2
Ur =
r
Nng lng ton phn:
E r = Tr + U r =
Ze 2 Ze 2
Ze 2
=
2r
r
2r
Electron gim bn knh mt cch lin tc, electron s ri vo ht nhn!
1.3. Hm sng, phung trnh sng Schrdinger

C hc lng t tha nhn (tin 1): Mi trng thi ca h vt l vi m
c t trng bng mt hm xc nh ph thuc vo to v thi gian (r,t)
c gi l hm sng hay hm trng thi. Mi thng tin v h lng t ch c
th thu c t hm sng (r,t) m t trng thi ca h.
Phng trnh sng Schrdinger c dng:
8 2 m
+
( E U ) = 0
h2
2
(1)
__________________________________________________________________________________________
TS. L Minh c
2 =
2
2
2
+
+
x 2 y 2 z 2
(Ton t Laplace)
l hm sng m t trng thi dng. Hm sng l mt hm to khng

gian (x,y,z); m: khi lng h; E: nng lng ton phn, U=U(x,y,z): ni
nng.
Gii phng trnh Schrdinger tm c hm sng (hm ring) c trng
cho trng thi dng v gi tr nng lng E (tr ring) tng ng.
Xc sut tm thy vi ht trong phn th tch dV chung quanh mt im no
trong khng gian:
2
d = dV = . * .dV
(2)
d
2
=
dV
V mt xc sut:
Nu ly tch phn trong ton b khng gian, th xc sut ny s bng 1
| |
dv = 1
(3)
y l iu kin chun ho ca hm sng, hm sng tho mn iu kin

ny c gi l hm nh chun hay hm chun ho.
Hm sng cn tho mn cc iu kin sau:
- l hm gii ni v sc xut khng phi l v tn
- l n tr
- lin tc v mt sc xut l lin tc
1.3.1. Hm sng ton phn, i xng, phn i xng
Trng thi ca h c m t bng hm sng trng thi dng (qi,qk),
ph thuc to ca hai vi ht i v k. Khi hai ht i v k i ch cho nhau hm
sng tng ng l (qi,qk) v (qk,qi).
Theo nguyn l khng th phn bit cc vi ht th trng thi ca h trc v
sau khi i ch l khng thay i, tc l sc xut tng ng s khng thay i.
2 (qi , q k ) = 2 (q k , qi )
(4)
__________________________________________________________________________________________
TS. L Minh c
(qi , q k ) = (q k , qi )
(5)
(qi , qk ) = (qk , qi )
(6)
Hm sng (6) khng i du khi cc ht i ch, gi l hm sng ton

phn i xng. Hm sng (7) l hm sng ton phn phn i xng. Nu c N
vi ht, hm sng ton phn l (q1,q2,q3, . . .,qN), s c N! ln i ch.
1.3.2. Nguyn l chng cht cc trng thi
Nu h lng t c th nhng trng thi m t bi nhng hm sng 1,
2, 3 . . . th n cng c th trng thi biu din bi mt hm sng vit
dng t hp tuyn tnh ca cc hm sng trn
= C1 1 + C 2 2 + ... + C n n
1.4. Ton t trong c hc lng t

1.4.1. Cc nh ngha v ton t
Ton t l mt k hiu tc ng ton hc tng qut L . Khi thc hin ln
mt hm s u(x1,x2, . . .,xn) c cc bin s x1, x2,. . . , xn th s thu c mt hm
sng mi v(x1,x2, . . .,xn) cng ph thuc x1,x2, . . .,xn.
L u(x1,x2,. . .,xn) = v(x1,x2, . . .,xn)
;
V d : L =
x
u(x)=x2 + a
L = ( x 2 + a ) = 2 x = u ( x)
x
Ton t tuyn tnh: L gi l tuyn tnh nu tho mn iu kin

L (C1u1 + C2u2 +. . .+ Cnun) = C1 L u1 + C2 L u2 + . . . = C1v1 + C2v2 + . . .
u1, u2, . . . l cc hm bt k
C1, C2, . . . l cc h s
Ton t loi ny : php nhn, vi phn cp 1, 2, . . .
Tng cc ton t: Tng cc ton t A , B l mt ton t C sao cho
kt qu tc dng ca n ln mt hm tu bng tng cc kt qu tc dng cc
cc ton t ln hm .
__________________________________________________________________________________________
TS. L Minh c
=A
+B
u = A
u +B
nu C
u
C
Tch cc ton t: tch hai ton t A , B l ton t C hoc C' sao cho
u = A
(B
u)
C
'u = B
u)
(A
C
Ton t tuyn tnh t lin hp

L gi l ton t tuyn tnh lin hp nu tho mn
u L.u dx = u
*
1
.L* u 1*dx
u1* l lin hp phc ca u1, L* l lin hp phc ca L .
V d :
d
L = i.
dx
th L* = i.
d
dx
Ton t to
x = x, y = y , z = z
L u = xu = xu
L =x,
V d :
Ton t ng lng
K hiu p , p = i.h.
Vi h =
h
; = + + (ton t Nabla)
x y z
2
Ton t ng lng c cc thnh phn

p x = i.h.
;
x
p y = i.h.
;
y
p z = i.h.
(7)
Ton t ng nng
Cc ht v m, ng nng xc nh bi
mv 2
1
T=
=
(p 2x + p 2y + p 2z )
2
2m
Kt hp cng thc trn ta c

T =
1 2
2
2
h2 2
h2
( 2 + 2 + 2 )h 2 =
=
2
2m x
2m
y
z
8. 2 .m
Ton t th nng
u = u ( x, y , z )
__________________________________________________________________________________________
TS. L Minh c
Ton t nng lng ton phn

Nng lng ton phn bng tng ng nng v th nng
H = T + U =
Ta c :
h2
8. .m
2
H l ton t Hamilton
2 + U ,
2 +
H = E.
8 2 m
( E U ). = 0
h2
Phng trnh Schrdinger
1.4.2. Biu din mt i lng vt l

Tha nhn cc tin
Tin 2: ng vi mt i lng c hc L c mt ton t lin hp L tc
dng ln hm sng . Khi gia cc ton t cng c nhng h thc ging nh
cc h thc gia cc i lng c in.
Tin 3: Tp hp nhng tr ring ca ton t L l ng nht vi tp hp
tt c nhng gi tr kh d ca i lng c hc L.
Tin 4: mt trng thi ca h lng t c trng bng hm sng
th gi tr trung bnh L ca mt i lng c hc L (to , ng lng . . .)
c xc nh:
L = * L dx
Theo tnh cht lin hp:
L = L * * dx
(8)
L* = * L dx
V do
(9)
L =L*
Vy mt i lng vt l c biu din bng mt ton t tuyn tnh t

lin hp th l mt i lng thc.
1.4.3. Phng trnh ton t tng qut
Mun xc nh c i lng vt l no ca h vi ht, thay L bng
ton t tng ng vo phng trnh:
L = L
__________________________________________________________________________________________
TS. L Minh c
V d : tm E, thay L bng ton t Hamilton. Phng trnh thng l

phng trnh vi phn tuyn tnh thun nht c nhiu nghim. Hm phi tho
mn cc iu kin: gii ni, n tr v lin tc c gi l cc hm ring ca
ton t L . Gi tr L tng ng vi mi hm ring gi l tr ring.
__________________________________________________________________________________________
TS. L Minh c
2. CHNG 2: CU TRC ELECTRON NGUYN T

2.1. Nguyn t H v ion ging H
2.1.1. Phng trnh Schrdinger
Gi M l khi lng ca ht nhn nguyn t; Ze l in tch, Z l s th t
trong nguyn t trong bng h thng tun hon, m l khi lng ca electron c
in tch l e.
Tng tc ht nhn-electron: U r =
Ze 2
r
M >>me nn xem ht nhn ng yn, electron chuyn ng. Phng trnh

Schrdinger tng qut
8 2 m
Ze 2
+
(E +
) = 0
r
h2
2
U(r) ch ph thuc khong cch ht nhn-electron. Biu din to

(r,,) thay cho to cu.
2
2 8 2 m
1
1 2 d
1
(r
)+ 2
(sin
)+ 2
+
( E + e ) = 0
2
2
2
r r
r
r
h
r sin
r sin
ph thuc r, , :
( r , , ) = R ( r ).( ). ( )
2.1.2. Orbital nguyn t (AO)

Hm sng nlm (r , , ) = Rnl (r ).Ylm ( , ) m t chuyn ng ca mt electron
trong trng lc ht nhn nguyn t c gi l orbital nguyn t (Atomic
orbital-AO). Hm sng c trng bng tp hp 3 s lng t n, l, m.
-Mt gi tr ca n th c n2 hm sng ( n2 AO), ng vi mc nng lng
En =
13,6
(eV )
n2
-Mt gi tr ca l c 2l+1 gi tr ca m, ng vi 2l+1 hm sng

-Trng thi c nhiu hm sng ng vi mt mc nng lng gi l trng
thi suy bin. S hm sng gi l suy bin.
__________________________________________________________________________________________
TS. L Minh c
Bng 1.1: Cc hm sng ca nguyn t H (vi n = 1, 2, 3)
2.1.3. Spin v nng lng electron

Gii phng trnh Schrdinger xut hin 3 s lng t n, l v m. Tuy nhin
tp hp ny cha th m t y trng thi ca in t trong nguyn t.
__________________________________________________________________________________________
TS. L Minh c
10
gii thch cu to kp ca vch quang ph, nm 1925 Uhlenbeck v

Goudsmit a ra gi thuyt v spin v a thm vo s lng t spin m t
trng thi ca in t. Theo h, ngoi momnen ng lng c xc nh bng
s lng t l, in t cn c momen ng lng ring hay momen spin.
Nm 1928, Dirac (Anh) da vo thuyt tng i ca Einstein, tng i
ho c hc lng t v gii thch s tn ti ca spin. Mt vi kt qu c th
hin:
+Momen spin c xc nh: M s = s(s + 1) .h vi s=1/2
Hnh chiu Ms(z) ca Ms ln phng Z ca trng lc ngoi
M s ( Z) = m s .h vi ms =1/2 = s
+Momen ng lng ton phn Mtp: xc nh bi s lng t ni j

M tp =
j( j + 1)h vi
j=l s
j=l 1/2: momen ng lng orbital v spin l song song nhau

j=l 1/2: momen ng lng ngc chiu nhau
S c mt ca spin nn mi mc nng lng En,l c tch thnh 2 phn
mc nm k nhau
Enj
Enl
Enj
+Momen t orbital
e =
:manheton Bohr
+Momen t spin e
e
eh
Ml =
2m e
2.m e
l(l + 1) = l(l + 1)
e.h
2.m e
e =
e
Ms
2m e
__________________________________________________________________________________________
TS. L Minh c
11
Nng lng ca electron khng tnh n spin

En =
Khi tnh n spin
2. 2 .me .e 4
n 2 .h 2
2. .me .e 2
E nj =
1 +
n
n 2 .h 2
1
3
j + 1 4.n
2. .e 2
1
=
h s cu trc tinh vi
h.c
137
Enj ph thuc s lng t ni j, j. Khi e chuyn ng t mc n n n:

=
En' j '
hc
E nj
hc
= Tn ' j ' Tnj
Vi quy tc l = 1; j = 0,1
Tnj (Tnj): s hng quang ph
Khi c chuyn ng t quay quanh trc ca electron (c trng bng s
lng t spin ms khc ), hm sng ton phn s c biu din bng mt tp
hp 4 s lng t: m, n, l v ms - ph thuc vo to khng gian (r, , ) v
to spin
n l m ms (r, , , ) = a(q)
Do 2 electron chuyn ng c lp nn c th tch lm 2 hm
n l m ms (r, , , ) = (r, , ).ms()
ms() khng phi l mt hm ton hc. Nh vy vi mt hm to
khng gian n l m s c hai orbital ton phn n l m 1/2 v n l m -1/2
2.2. Nguyn t nhiu electron

2.2.1. M hnh h cc electron c lp
Tha nhn: Mi electron chuyn ng c lp vi cc electron khc trong
mt trng trung bnh c i xng cu (trng xuyn tm) c to ra bi ht
nhn v cc electron khc.
__________________________________________________________________________________________
TS. L Minh c
12
r r r r
Vi n electron c lp, hm sng m t l (r1 , r2 , r3 ...rn ) tho mn phng

trnh Schrdinger H = E
H = T + U
n
T =
i
r r r
r
h2
2
2
2
2
2
,
, u = u (r1 , r2 , r3 ,..., rn )
=
+
+
i
i
2
2
2
2
8 me
xi y i z i
Electron chuyn ng c lp nn
r r r
r
r
r
r
u = u (r1 , r2 , r3 ,..., rn ) = 1 (r1 ).2 (r2 )...n (rn )
H = H 1 + H 2 + ... + H n
E = E1 + E 2 + ...E n
Mi electron i chuyn ng tng ng vi phng trnh Schrdinger

r
r
H i i (ri ) = Ei i (ri )
H i =
r r
r
h2
2 + u i (ri )
2
8 me
Hm (r1 , r2 ,...rn ) khng phi l AO, cha phn nh spin

(q1 , q 2 ,..., q n ) = a1 (q1 ).a2 (q 2 )...an (q n )
2.2.2. Hm sng ton phn

Hm sng ton phn ca h 2 electron a1(q1), a2(q2)
I (q1 , q 2 ) = a1 (q1 ).a2 (q 2 )
Khi i ch 2 electron
II (q 2 , q1 ) = a1 (q 2 ).a2 (q1 )
Theo nguyn l chng cht trng thi

(q1 , q 2 ) = C1 I + C 2 I I = C1 a1 (q1 ).a 2 (q 2 ) + C 2 a1 (q 2 ).a 2 (q1 )
H ang xt l cc ht fermi, nn hm sng ton phn m t trng thi ca

h phi l hm phn i xng.
(q1 , q 2 ) =
1
[a1 (q1 ).a 2 (q 2 ) a1 (q 2 ).a 2 (q1 )]
2
Khi 2 electron i ch
__________________________________________________________________________________________
TS. L Minh c
13
(q1 , q 2 ) =
[a1 (q 2 ).a2 (q1 ) a1 (q1 ).a 2 (q 2 )]
(q1 , q 2 ) = (q 2 , q1 )
Hoc c biu din dng nh thc

(q 1 , q 2 ) =
1 a1 (q 1 ) a1 (q 2 )
2 a 2 (q 1 ) a 2 (q 2 )
Nu c n electron c lp, nh thc cp n s l
(q1 , q 2 ,.., q n ) =
1
n!
a1 (q1 ) a1 (q 2 )... a1 (qi )... a1 (q n )

a 2 (q1 ) a 2 (q 2 )... a 2 (qi )... a 2 (q n )
an (q1 ) an (q 2 )... an (qi )... an (q n )
nh lut Slater:
-m bo hm sng ton phn l phn i xng
-Phn nh nguyn l Pauli dng tng qut: Trong mt nguyn t, khng
th c hai (hay nhiu) electron m trng thi ca chng c trng bng cng mt
tp hp 4 s n, l, m, ms ging nhau.
__________________________________________________________________________________________
TS. L Minh c
14
2.2.3. Nguyn tc nghin cu h nhiu electron

z
H = Te + U en + U ee
rij
ri
Te =
rj
h2
8 2 me
i =1
i =1
i2 ; U en =
Ze 2
ri
e2
e2
U ee = r r =
rij
i # j | ri r j |
x
y
Cc phng php gii gn ng phng trnh Schrdinger

Phng php nhiu lon (Pertubation method)
-Gn ng cp 0: b qua tng tc ca electron vi nhau.
-Gn ng cp 1: cc hm sng thu c t gn ng cp 0 s dng tnh
nng lng tng tc trung bnh gia cc electron.
dV = U dv =
U ee = * U
ee
ee
e2 2
dv
rij
V d: vi He (z=2), th nng ca h
2e 2 2e 2 e 2
U =
+
r1
r2
r1, 2
Gii gn ng cp 0: U =
2e 2 2e 2
r1
r2
Vi electron th nht
;
H 1 =
h2
2e 2
2
1
r1
8 2 me
H 2 2 = E 2 2 ;
H 2 =
h2
2e 2
2
2
r2
8 2 me
H 1 1 = E1 1
Nng lng ton phn ca h gn ng cp 0: E 0 = E1 + E 2 , tng ng hm

r
sng (r1 , r2 ) = 1 (r1 ).2 (r2 ) .

Nu gii hm gn ng cp 1, nng lng ton phn ca h E = E 0 + U ee
hm sng vn gi nguyn nh gn ng cp 0.
Phng php trng t hp (self-consistent field)
Ni dung ca phng php
__________________________________________________________________________________________
TS. L Minh c
15
-Hm ring ca h n electron bng tch cc hm ring ca tng electron.

r r r
r
r
r
r
= (r1 , r2 , r3 ,..., rn ) = 1 (r1 ).2 (r2 )...n (rn )
-Hm ring v nng lng ca electron c xc nh trong trng to ra

bi ht nhn v electron cn li.
r r
Th nng ca electron i c xc nh U i (ri , r j ) =
Ze 2
e2
+
electron i
ri
i # j ri j
khng trong trng xuyn tm.

electron i trong trng xuyn tm:
-Trung bnh ho th nng Uee
U ee =
i# j
2
e2
e2
=
j (r j ) dv
rij i # j ri j
2
r
Ze 2
e2
+
j (rij ) dv
U i (ri ) =
ri
ij rij
(10)
Nh vy ch cn ph thuc khong cch t electron i n ht nhn. Cc

electron j c th trng thi khc p, d, f . . .cha th i xng cu, trung bnh
r
ho U i (ri ) theo gc
U (ri ) =
1
U i (ri )d
4
(11)
U (ri ) l th nng ca trng i xng cu (xuyn tm) - tng hp trng
ht nhn v trng cc electron trung bnh ho theo v tr ca cc electron v

theo gc.
Ton t Hamilton ca electron i s l:
H i = Ti + U i (ri ) =
h2
i2 + U i (ri )
2
8 me
Phng trnh Schrdinger m t chuyn ng ca electron i

H i i = E i i
(12)
V l trng xuyn tm nn i (ri ) c th tch ra

i (ri ) = Rnl (ri ). lm ( ). m ( ) = Rnl (ri ).Ylm ( , )
__________________________________________________________________________________________
TS. L Minh c
16
Ylm ( , ) ging nh phn gc ca cc AO trong nguyn t H v cc ion
ging H.
xc nh cc AO ca electron i trong nguyn t nhiu e, ta ch cn xc
nh phn bn knh Rnl (ri ) - c trng tng tc gia electron i vi cc electron
khc.
Xc nh i (ri ) :
-Chn hm sng ring ca electron trong nguyn t H l hm ban u thay
vo 14, 15 tm c th nng U(ri).
-Thay U(ri) vo 16 tm c hm ring i (ri ) ca electron i.
Hm i (ri ) tm c s khc vi hm ban u, s cho kt qu gn ng tt
hn. Qu trnh ny lp i lp li cho n khi hm ring ca electron i tm c
ln cui trng vi hm ring ca n oc xc nh ngay ln trc .
Phng php ny c Hartree xy dng nm 1925, Fock ci tin nm
1930 v c gi l phng php trng t hp Hartree Fock.
__________________________________________________________________________________________
TS. L Minh c
17
3. CHNG 3: CU TO PHN T - LIN KT HO HC

3.1. Kho st lin kt CHT trn c s lng t
Ho hc xy dng trn c s ho lng t c gi l Ho lng t. C
hai phng php ho hc lng t dng kho st lin kt cng ho tr l
phng php VB (Valence Bond) v phng php MO (molecular orbital).
Mc ch ca hai phng php: xc nh gi tr nng lng v cc hm
sng tng ng ca phn t t cc hm sng mt electron nguyn t qua vic
gii phng trnh Schrdinger cho h phn t.
3.1.1. Hn ch ca cc thuyt c in v lin kt ho hc v cu to
phn t
-Cc thuyt c in khng gii thch cc trng hp vi phm quy tc bt t
V d: trong NO, N c 7 electron; trong BN B c 6 electron; PF5 P c 10
electron.
-Ho hc c in gp kh khn trong vic vit cng thc cu to ca nhiu
hp cht khc nhau, c bit l i vi cc hp cht c lin kt .
-Khng th gii thch c trng hp cc hp cht tha, thiu electron.
Thiu electron trong B2H6. Tha electron trong XeF2.
-i vi lin kt ion, thuyt c in ch gii thch c ngun gc ca lc
ht. Thc cht tn ti khong cch khng i gia cc ion , chng t c s
cn bng gia lc ht v lc y.
-Thuyt c in khng gii thch c nhiu tnh cht ca kim loi.
-Thuyt c in khng gii thch tng tc gia cc phn t khng cc c
bit l cc nguyn t kh tr.
-Thuyt c in phn bit 4 loi lin kt nhng thc t, lin kt ho hc
trong hu ht cc cht u l s t hp hoc l dng trung gian gia cc m hnh
gii hn.
__________________________________________________________________________________________
TS. L Minh c
18
-Cc thuyt c in khng gii thch c cc vn c bn ca lin kt

nh: bn cht ca lin kt cng ho tr, tnh s nguyn, bo ho ho tr, tnh nh
hng cc ho tr ca nhiu nguyn t ho hc.
-Khng gii thch c ti sao c nhng phn t m lin kt c to thnh
bng mt s l electron.
3.1.2. Kho st lin kt ho hc v cu to phn t trn c s Ho
lng t
Phn t l mt h phc tp v cha nhiu electron nn vic gii chnh xc
phng trnh Schrdinger l khng th. Phng trnh ch c gii bng phng
php gn ng.
Gn ng Born-Oppenheimer: i vi phn t, khi lng ht nhn ln
hn nhiu so vi khi lng ca electron nn ch kho st s chuyn ng ca
ht nhn v electron mt cch c lp nhau. Electron chuyn ng trong trng
lc ca ht nhn ng im, cch ht nhn mt khong R. Nng lng E v ton
t H khng ch ph thuc vo electron m cn v tr ca ht nhn.
Cc php tnh gn ng ton hc: php nhiu lon, phng php bin phn.
3.2. Phng php lin kt ho tr

3.2.1. Gii phng trnh Schrdinger
3.2.1.1. Phng trnh
Heitler v London (nm 1927) p dng phng php c hc lng t gn
ng phng php nhiu lon vo trng hp lin kt cng ho tr ca
Phng trnh Schrdinger cho h nhiu electron
H = E
r12
r1b
2
r2a
H =
h2
(12 + 22 ) + U
2
8 me
12 =
2
2
2
+
+
x12 y12 z12
22 =
2
2
2
+
+
x 22 y 22 z 22
__________________________________________________________________________________________
TS. L Minh c
19
Th nng ca h gm cc tng tc tnh in sau

u1a =
e2
- th nng ht gia electron 1 v nhn a
r1a
u 2b =
e2
- th nng ht gia electron 2 v nhn b
r2b
u 2a =
e2
- th nng ht gia electron 2 v nhn a
r2 a
u1b =
e2
- th nng ht electron 1 v nhn b
r1b
u12 =
e2
- th nng y gia electron 1 v 2
r12
u ab =
e2
- th nng y gia hai nhn a v b
R
U = U o + U ' = e 2 (
1
1
1
1
1 1
+
+
+
)
r1a r2b r1b r2 a r12 R
Vi Uo th nng ht gia electron v ht nhn trong hai nguyn t hydr;

U l th nng tng tc gia hai nguyn t H.
h2
2
8 me
2
2
2
2
2
2
2 + 2 + 2 + 2 + 2 + 2
x1 y1 z1 x 2 y 2 z 2
2 1
1
1
1
1 1
e ( +
+
+
) = E
r1a r2b r1b r2 a r12 R
3.2.1.2. Gii phng trnh

-Gn ng cp 0:
Ch n Uo v b qua U. Th nng ca h
U o = u1a + u 2b = e 2 (
1
1
+ )
r1a r2b
Nng lng ton phn ca h trng thi c bn (n=1)

E o = E1 + E 2 =
4 2 me e 4
h2
Xc sut tm thy electron ng thi c hai electron trong 2 trng ht nhn

l s kin xy ra ng thi. Gi I l hm sng ca h th:
2
I (1,2) = a (1) b (2)
__________________________________________________________________________________________
TS. L Minh c
20
I (1,2) = a (1).b (2)
Khi hai electron i ch cho nhau:

2
II (2,1) = a (2) b (1)
Do :
II (2,1) = a (2).b (1)
Hm sng m t bng t hp tuyn tnh ca I v II :

= (1,2) = C1 I (1,2) + C 2 II (2,1) = C1 a (1).b (2) + C 2 a (2).b (1)
iu kin E t cc tiu: C1 = C 2
Khi C1 = C 2 = N s
s = N s (I + II ) = N s [a (1).b (2) + a (2).b (1)] - hm i xng
Khi C1 = C 2 = N a
a = N a (I II ) = N a [a (1).b (2) a (2).b (1)] - hm phn i xng
Tm li bi ton phn t H2 gn ng cp 0:
H o E = E o
H o =
h2
(12 + 22 ) + U o
2
8 me
Nhn hai v ca phng trnh Schrdinger trong gn ng cp 0 vi ri

ly tch phn:
H
E
dv = E o 2 dv
H
=
dv
dv
-Gn ng cp 1
Trong gn ng cp 1, c tnh n tng tc gia hai nguyn t H.
H = E
H =
h2
(12 + 22 ) + U o + U '
2
8 me
H = H 0 + H '
__________________________________________________________________________________________
TS. L Minh c
21
H dv ( H + H ' )dv H
=
=
E=
dv
dv
0
2
dv
dv
H ' dv
=E
+
dv
H ' dv
+
dv
2
E c hai gi tr tng ng vi hai hm s v a

Es = E 0 +
K+A
1+ S 2
Ea = E0 +
KA
1 S2
1
1
1 1
K = e 2
+ + a2 (1).b2 (2).dv - tch phn Coulomb
r1b r2a r12 R
1
1
1 1
A = e 2
+ + a (1).b (2) a (2)b (1).dv - tch phn trao i
r1b r2a r12 R
S = a (1).b (1).dv = a (2).b (2).dv - tch phn xen ph
Mc xen ph ph thuc vo khong cch R gia hai ht nhn v t l vi

tch a .b . Khi R = , nng lng ca h bng tng nng lng ca hai nguyn
t H c lp. Khi R=0, hai ht nhn a v b trng nhau.
S = a .b .dv = a2dv = b2dv = 1 - iu kin chun ho hm sng.
E(R)
Ea
(1)
R
(3)
R0
(2)
Es
S ph thuc ca E vo R
ng cong (2), hai nguyn t H y nhau, tng ng vi hm sng i
xng. ng (3) ng vi hai nguyn t ht nhau mnh nht, to lin kt phn
t.
__________________________________________________________________________________________
TS. L Minh c
22
3.2.2. Bn cht lin kt cng ho tr

Hm sng khi xt n spin. Hm sng ton phn
(1,2) = (1,2). (1,2)
Ging nh hm to khng gian, hm spin cng c tnh i xng v phn

i xng
s (1,2) = s (2,1)
; a (1,2) = a (2,1)
Theo nguyn l Pauli, hm sng ton phn phi l hm i xng

(1,2) = (2,1) .
Nu bnh phng hai v ca s v a :

s2 = N s2 (I2 + 2I II + II2 )
a2 = N a2 (I2 2I II + II2 )
Trong trng hp lin kt, xc sut tm thy electron vng gia hai ht
nhn tng ln mt lng 2I .II so vi I2 + II2 , tng in tch ca m my
electron, hai ht nhn ht li vi nhau, tng lin kt.
Vi hm a , mt electron s gim i mt lng 2I .II so vi I2 + II2 .
Do hai ht nhn y nhau, lin kt khng c to thnh.
Vy, bn cht ca lin kt cng ho tr l tng tc tnh in gia hai ht
mang in tch (ht nhn v electron).
3.3. Phng php orbital phn t (MO)

Nhng hn ch ca phng php lin kt ho tr hay phng php cp
electron:
-Trong mt s trng hp, lin kt c th to bi 1 electron.
-Trong mt s phn t: NO, NO2, ClO2, O2 . . . hoc cc gc t do vn cn
cha cc electron t do.
Phng php orbital phn t do Mulliken, Hund, Hecbe v Lenard-Jones
(M) xy dng nm 1927.
__________________________________________________________________________________________
TS. L Minh c
23
3.3.1. Phng php t hp tuyn tnh cc AO (Linear Combination of

Atomic Orbital - LCAO)
Tng t AO, MO (molecular orbital) c nh ngha l hm sng to
khng gian mt electron m t trng thi chuyn ng ca tng electron trong
trng lc ca nhiu ht nhn nguyn t trong phn t.
T hp tuyn tnh cc AO:
(13)
= C1 1 + C 2 2 + ... + C n n
1 , 2 ,..., n l cc AO bit. C1, C2,,Cn l cc h s cn xc nh.
Mi orbital phn t c nng lng

H dv
E=
dv
2
Thay vo biu thc trn, E s l mt hm ca cc bin s C. Nng lng

ca MO trng thi c bn phi l cc tiu
E
E
E
= 0;
= 0;....;
=0
C1
C 2
C n
n gin, xt trng hp n=2, tc MO l t hp ca hai hm sng AO

= C1 1 + C 2 2
E
E
= 0;
=0
C1
C 2
E=
(C
1
+ C 2 2 )H (C1 1 + C 2 2 )dv
(C
1
E=
+ C 2 2 ) dv
2
C12 1 H 1 dv + C1C 2 1 H 2 dv + C1C 2 2 H 1 dv + C 22 2 H 2 dv

C12 12 dv + 2C1C 2 1 2 dv + C 22 22 dv
H 11 = 1 H 1 dv
H 12 = 1 H 2 dv = 2 H 1 dv = H 12 ( H l ton t lin hp)
H 22 = 2 H 2 dv
S11 = 1 1 dv = 12 dv
__________________________________________________________________________________________
TS. L Minh c
24
S12 = 12dv = S
S 22 = 2 2 dv = 22 dv
Thay vo trn ta c:
E=
C12 H11 + 2C1C 2 H 12 + C 22 H 22

C12 S11 + 2C1C 2 S12 + C 22 S 22
E C12 S11 + 2C1C 2 S12 + C 22 S 22 = C11 H 11 + 2C1C 2 H 12 + C 22 H 22
Ly o hm theo C1 vi iu kin
E
=0
C1
Ta c: (H 11 ES11 )C1 + (H 12 ES12 )C 2 = 0

Hon ton tng t ly o hm theo C2 vi iu kin
E
=0
C 2
Ta c: (H 21 ES 21 )C1 + (H 22 ES 22 )C 2 = 0
Ta c h phng trnh xc nh C1 v C2
(H 11 ES11 )C1 + (H 12 ES12 )C 2 = 0
(H 21 ES 21 )C1 + (H 22 ES 22 )C 2 = 0
Nghim tm thng C1=C2=0 (trivial solution). Nu nh thc khc 0, theo

quy tc Cramer, nghim C1=C2=0 (c mt ct bng 0). nghim khng tm
thng, nh thc bng 0.
H 11 ES11 H 12 ES12
H 21 ES 21 H 22 ES 22
=0
Gii phng trnh ny ta c c gi tr ca E.

Trong trng hp tng qut khi MO c t hp t n orbital
(H 11 ES11 )C1 + (H 12 ES12 )C 2 + ... + (H 1n ES1n )C n = 0
(H ES )C + (H ES )C + ... + (H ES )C = 0
21
21
1
22
22
2
2n
2n
n
...............................................................................................
(H n1 ES n1 )C1 + (H n 2 ES n 2 )C 2 + ... + (H nn ES nn )C n = 0
__________________________________________________________________________________________
TS. L Minh c
25
(H 11 ES11 ) + (H 12 ES12 ) + ... + (H 1n ES1n )

(H 21 ES 21 ) + (H 22 ES 22 ) + ... + (H 2 n ES 2 n )
.............................................................................
(H n1 ES n1 ) + (H n 2 ES n 2 ) + ... + (H nn ES nn )
=0
3.3.2. Phng php MO cho hai nguyn t ging nhau

3.3.2.1. Bi ton H 2+
Trong h ny, electron c th c cc v tr
e
r2
- r1
1
-electron gn ht nhn 1, chu nh hng ca ht nhn 1(hnh a, r1<r2)

-electron gn ht nhn 2, chu nh hng ca ht nhn 2 (hnh b, r1>r2).
-electron chu nh hng ng thi ca hai ht nhn 1 v 2 (hnh c).
Theo nguyn l chng cht trng thi
= C1 1 + C 2 2
Mc ch ca bi ton:
-Tm C1, C2 tho iu kin cc tiu nng lng E, t bit c .
-Tnh gi tr nng lng E ca MO (hm sng )
Trong trng hp, hai nguyn t ging nhau, H11=H22, H12=H21, cc tch
phn xen ph S
S11 = 12 dv = 1
; S 22 = 22 dv = 1
Do :
(H 11 E )C1 + (H 12 ES )C 2 = 0
(H 12 ES )C1 + (H 11 E )C 2 = 0
H 11 E
H 12 ES
H 12 ES
H 11 E
=0
(H 11 E )2 (H 12 ES )2 = 0
__________________________________________________________________________________________
TS. L Minh c
26
Nng lng ca MO l
E=
H 11 H 12
1 S
H 11 = 1 H 1 dv l tch phn Coulomb

H 12 = 1 H 2 dv tch phn cng hng (tch phn trao i)
S = 1 2 dv tch phn xen ph
*Gi s electron chu nh hng ca ht nhn 1

H =
h2
e2 e2 e2
2
+
r1 r2
R
8 2 me
Ton t H biu din nng lng ca electron trong trng ht nhn s tr

thnh ton t biu din nng nng lng ca electron trong nguyn t H.
H H =
H 11
h2
e2
2

r1
8 2 me
1 dv
2
1
dv
= EH
(R )
*Vi tch phn S

Thay bng cc biu thc hm sng ca H trng thi 1s
1 =
e r1 ; 2 =
e r 2 . Sau khi ly tch phn, ta c

S = e R (1 + R +
R2
)
3
Trng thi thc ca H 2+ ng vi gi tr ca S trong khong 0 S 1

*Vi tch phn H12
Muliken tm c mi lin h sau
H 12 = kE H 1 2 dv = k E H S
Khi R th S=0, ta c: H 12 = 0
Tm li: khi R th
__________________________________________________________________________________________
TS. L Minh c
27
H 11 = E H
S =0
E=
H 12 = 0
H 11 H 12
= H 11 = E H
1 S
Trng thi nng lng ca H 2+ bng nng lng ca electron trong H gi l

trng thi khng lin kt.
Khi 0 < R < ; S > 0 , tnh ton cho bit H 11 < 0; H 12 < 0 nn
E1 = E lk =
H 11 + H 12
< EH
1+ S
Ngha l nng lng ca H 2+ thp hn nng lng trong H. E1 l nng

lng ca electron trng thi lin kt. H 2+ tn ti bn hn.
Ngc li, E 2 = E plk =
H 11 H 12
> E H lc ny nng lng electron trong
1 S
H 2+ ln hn nng lng electron trong H. Trng thi ny gi l trng thi phn
lin kt.
*Orbital phn t trng thi lin kt v phn lin kt
Tng ng vi Elk v Eplk s c hai orbital phn t lin kt v phn lin kt.
T phng trnh trn ta c
C1
H ES
= 12
C2
H 11 E
Thay E bng Elk:

H + H 12
H 12 11
S
H S H 12
C1
1+ S
=
= 11
=1
H 11 S H 12
C2
H 11 + H 12
H 11
1+ S
Vy C1 = C 2 N lk gi l h s chun ho ca hm sng lin kt lin kt

lk = N lk (1 + 2 )
T iu kin chun ho hm sng
2
2
2
2
2
2
lk dv = N lk (1 + 2) .dv = N lk 1 dv + 2 1 .2 .dv + 2 dv = 1 = N lk (2 + 2S )
2
Suy ra
N lk =
1
2(1 + S )
; lk =
1
2(1 + S )
(1 + 2 )
__________________________________________________________________________________________
TS. L Minh c
28
Khi thay E bng Eplk th C1 = C 2 = N plk

plk = N plk (1 2 ) =
1
2(1 S )
(1 2 )
trng thi lin kt: mt electron vng gia hai ht nhn tng ln, hai
ht nhn ht mnh lm gim nng lng electron trn orbital phn t lin kt
so vi trn orbital nguyn t trong H, do lin kt c hnh thnh.
Ngc li, hm sng phn lin kt, mt electron gia hai nhn gim,
nng lng electron trn orbital phn t phn lin kt cao hn trong nguyn t
H, do lin kt khng c hnh thnh.
3.3.2.2. iu kin cc AO t hp to thnh MO
-Nng lng ca cc AO phi gn bng nhau.
-Cc hm sng AO phi xen ph mnh
-Cc AO c cng mt tnh cht i xng vi ng ni cc ht nhn
nguyn t - trc lin kt.
__________________________________________________________________________________________
TS. L Minh c
29
3.3.3. Phng php MO cho hai nguyn t khc nhau

Nng lng ca cc AO cng loi ca hai nguyn t khc nhau s khc
nhau. Nguyn t no c m in ln hn thi AO s c nng lng thp hn.
Hm sng c biu din
lk = N lk ( A + B )
plk = N plk ( A B )
l h s khc 1, n c trng cho phn cc ca lin kt cng ho tr
__________________________________________________________________________________________
TS. L Minh c
30
S nng lng cc MO ca phn t AB (B>A)
3.3.4. Phng php MO phn t c nhiu nguyn t

Xt mt s v d in hnh
-Phn t BeH2
__________________________________________________________________________________________
TS. L Minh c
31
-Phn t BeF2
__________________________________________________________________________________________
TS. L Minh c
32
__________________________________________________________________________________________
TS. L Minh c
33
3.3.5. Phng php Hckel

3.3.5.1. Bi ton
Trong phng php Hckel cho rng:
-Tch phn trao i i vi hm sng khng ph thuc hai nguyn t k
nhau s bng 0.
-Tch phn vi hai nguyn t C k nhau th tch phn Coulomb s nh nhau
v tch phn trao i cng nh nhau.
-Tt c cc tch phn xen ph u bng 0.
3.3.5.2. Mt electron , bc lin kt v ch s ho tr t do
*Mt electron l i lng c trng cho s c mt ca electron
khng nh c nguyn t kho st. i lng ny c gi tr cng ln th
nguyn t tch in m cng nhiu.
Mt electron c tnh:
Xc sut gp electron trn MO :
j2 = C 2jr r2
r
j l hm sng phn t c t hp t cc orbital nguyn t r . Cjr l h
s ca hm sng nguyn t r
__________________________________________________________________________________________
TS. L Minh c
34
Khi electron trn MO j th C 2jr chnh l phn mt in tch electron

ti nguyn t r. Nu ly tng mt in tch theo tt c cc orbital j cha nj
electron th s c tng mt in tch electron (cn gi l mt
electron ) ti nguyn t r l qr.
q r = n j C 2jr
j
*Bc lin kt
Bc lin kt l k hiu Prs c trng cho mt in tch electron ca lin
kt v c xc nh bng biu thc:
Prs = n j C jr C js
j
Trong Cjr v Cjs l cc h s ca cc AO thuc 2 nguyn t r v s k

nhau to nn MO lin kt j (tc to nn lin kt ); nj l s electron trn MO lin
kt .
*Ch s ho tr t do
Ch s c tnh theo cng thc
F = N max N r
N r = Prs
F l ch s ho tr t do ca nguyn t, Nmax l gi tr cc i bc ca lin

kt m nguyn t cacbon c th tham gia to thnh. Nr l tng cc bc lin kt
m nguyn t r tham gia to thnh.
__________________________________________________________________________________________
TS. L Minh c
35
4. CHNG 4: I XNG
4.1. Khi nim
S phn b hnh hc ca ht nhn nguyn t c c trng bng di
lin kt, gc lin kt trong phn t. Mi phn t c cu trc hnh hc i xng
nht nh. Nhng cht c cng tnh cht i xng thng c nhng s cc s
hng ging nhau v nh tnh.
Cc mc nng lng ca nguyn t hay phn t c tnh ton y v
chnh xc bng i xng ca phn t. V vy, xem xt i xng, chng ta c th
ni c g y mt cch nh tnh. Cha tnh ton nh lng nhng chng ta
c th bit c c bao nhiu trng thi nng lng v cc tng tc gia chng.
Tuy nhin, ch xem xt i xng, chng ta khng th bit c iu g thc s
ang din ra. i xng, v nguyn tc, cho ta bit hai trng thi ca h khc
nhau v nng lng. i xng c th cho ta bit di hp th no y trong ph
in t hay dao ng ca phn t.
4.2. Cc php i xng c bn

4.2.1. Php quay quanh trc vi gc quay 2/n
Quay phn t mt gc bng 2/n chung quanh trc a cc ht nhn
nguyn t v v tr tng ng vi v tr ban u. Php quay ny gi l php
quay Cn, trc quay tng ng c gi l trc i xng bc n (k hiu l Cn).
Php quay c thc hin hai, ba,. . . ln c vit di dng
C n C n C n = C n3
Trong phn t c nhiu trc quay i xng, Trc quay c bc n ln nht

c gi l trc i xng chnh.
Php bin i ng nht E: tt c cc ht nhn nguyn t tr v li ng v
tr ban u (c th ni: php i xng khng lm g c !).
__________________________________________________________________________________________
TS. L Minh c
36
4.2.2. Php phn chiu qua mt phng

S phn chiu ca tt c cc nguyn t qua mt mt phng i qua phn t
c gi l php phn chiu, k hiu l . Mt phng ny l mt phng i xng
. C cc mt phng i xng: mt phng i xng thng gc v, nm ngang h,
v d chia i gc to bi hai trc C2.
__________________________________________________________________________________________
TS. L Minh c
37
4.2.3. Php phn chiu quay Sn

S t hp php quay Cn quanh mt trc i qua phn t v php phn chiu
cc nguyn t ti mt mt phng vung gc vi trc trn. K hiu l Sn.
K hiu: S n = C n n
4.2.4. Php chuyn o i

S phn chiu tt c cc nguyn t qua mt im gi l tm i xng. K
hiu S 2 = C 2 h = i
__________________________________________________________________________________________
TS. L Minh c
38
5. CHNG 5: M PHNG CU TRC PHN T

5.1. Gii thiu phn mm Gaussian 98
Phn mn Gaussian s dng d on nhiu tnh cht ca phn t, phn
ng nh:
-Nng lng v cu trc phn t
-Nng lng v cu trc ca cc trng thi chuyn tip
-Tn s dao ng
-Phn tch ph Raman v Hng ngoi IR
-Tnh cht nhit ho hc
-Nng lng lin kt v phn ng
-C ch phn ng
-Orbital phn t
-Momen lng cc
Phn mm s dng m phng phn t th kh hay th lng, trng thi
c bn hoc kch thch. Gaussian 98 l mt cng c mnh nghin cu nhiu lnh
vc ca ho hc nh hiu ng ca cc nhm th, c ch phn ng, xy dng b
mt th nng, nng lng kch thch.
5.2. Nhp lnh v chy chng trnh

Lnh c nhp vo bng cc k t m ASCII. Cu trc c bn ca lnh
gm cc phn sau:
__________________________________________________________________________________________
TS. L Minh c
39
-V tr v tn ca file nhp (scratch file)

-Phng php tnh
-Tiu ca bi tnh
-To ca cc nguyn t (Z-matrix)
V d:
%chk=water
#HF/6-31G(d) Freq, opt
Route section
Water energy
Title section
0 1
Molecule specification
O -0.464 0.177 0.0
(in Cartesian coordinates)
H -0.464 1.137 0.0

H 0.441 -0.143 0.0
5.3. Phn tch kt qu
__________________________________________________________________________________________
TS. L Minh c

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Bai giang

1. CHNG 1: C S HO LNG T ............................................... 1

3.2.1.2. Gii phng trnh 19

Ti liu tham kho

1.2. M hnh nguyn t Rutherford

ng nng ca electron c tnh: T = mv 2 =

Lc ht tnh in gia ht nhn v in t c tnh: F =

Gi A l cng cn thit di chuyn electron t khong cch r n v tn,

Ngc li, khi electron chuyn ng t n khong cch r i vi ht

Quy c U = 0 th th nng ca electron trn qu o vi bn knh r s l:

Nng lng ton phn:

Electron gim bn knh mt cch lin tc, electron s ri vo ht nhn!

1.3. Hm sng, phung trnh sng Schrdinger

l hm sng m t trng thi dng. Hm sng l mt hm to khng

Nu ly tch phn trong ton b khng gian, th xc sut ny s bng 1

y l iu kin chun ho ca hm sng, hm sng tho mn iu kin

Hm sng (6) khng i du khi cc ht i ch, gi l hm sng ton

1.4. Ton t trong c hc lng t

Ton t tuyn tnh: L gi l tuyn tnh nu tho mn iu kin

Ton t tuyn tnh t lin hp

u1* l lin hp phc ca u1, L* l lin hp phc ca L .

Ton t ng lng c cc thnh phn

Kt hp cng thc trn ta c

Ton t nng lng ton phn

Phng trnh Schrdinger

1.4.2. Biu din mt i lng vt l

Theo tnh cht lin hp:

Vy mt i lng vt l c biu din bng mt ton t tuyn tnh t

V d : tm E, thay L bng ton t Hamilton. Phng trnh thng l

2. CHNG 2: CU TRC ELECTRON NGUYN T

M >>me nn xem ht nhn ng yn, electron chuyn ng. Phng trnh

U(r) ch ph thuc khong cch ht nhn-electron. Biu din to

2.1.2. Orbital nguyn t (AO)

-Mt gi tr ca l c 2l+1 gi tr ca m, ng vi 2l+1 hm sng

Bng 1.1: Cc hm sng ca nguyn t H (vi n = 1, 2, 3)

2.1.3. Spin v nng lng electron

gii thch cu to kp ca vch quang ph, nm 1925 Uhlenbeck v

+Momen ng lng ton phn Mtp: xc nh bi s lng t ni j

j=l 1/2: momen ng lng orbital v spin l song song nhau

Nng lng ca electron khng tnh n spin

Khi tnh n spin

Enj ph thuc s lng t ni j, j. Khi e chuyn ng t mc n n n:

= Tn ' j ' Tnj

2.2. Nguyn t nhiu electron

Vi n electron c lp, hm sng m t l (r1 , r2 , r3 ...rn ) tho mn phng

Mi electron i chuyn ng tng ng vi phng trnh Schrdinger

Hm (r1 , r2 ,...rn ) khng phi l AO, cha phn nh spin

2.2.2. Hm sng ton phn

Theo nguyn l chng cht trng thi

H ang xt l cc ht fermi, nn hm sng ton phn m t trng thi ca

[a1 (q 2 ).a2 (q1 ) a1 (q1 ).a 2 (q 2 )]

Hoc c biu din dng nh thc

Nu c n electron c lp, nh thc cp n s l

a1 (q1 ) a1 (q 2 )... a1 (qi )... a1 (q n )

2.2.3. Nguyn tc nghin cu h nhiu electron

Cc phng php gii gn ng phng trnh Schrdinger

Nng lng ton phn ca h gn ng cp 0: E 0 = E1 + E 2 , tng ng hm

sng (r1 , r2 ) = 1 (r1 ).2 (r2 ) .

-Hm ring ca h n electron bng tch cc hm ring ca tng electron.

-Hm ring v nng lng ca electron c xc nh trong trng to ra

Th nng ca electron i c xc nh U i (ri , r j ) =

khng trong trng xuyn tm.

Nh vy ch cn ph thuc khong cch t electron i n ht nhn. Cc