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Kha lun tt nghip i hc 2011 GVHD: TS.

L Minh Hng

SVTH: Trn Nguyn Trang 1

MC LC
MC LC ................................................................................................................... 1
LI CM N ............................................................................................................. 3
DANH MC CC K HIU V CH VIT TT .................................................. 4
DANH MC CC BNG .......................................................................................... 5
DANH MC CC HNH V TH ..................................................................... 5
LI M U ............................................................................................................. 7
PHN 1- L THUYT M PHNG ....................................................................... 9
CHNG 1- C S L THUYT LNG T V L THUYT HARTREE
FOCK .......................................................................................................................... 9
1.1 Php gn ng Born- Oppenheimer ................................................................ 9
1.2. Nguyn l Pauli ............................................................................................. 10
1.3. Phng php Hartree ..................................................................................... 10
1.4. Phng php Hartree-Fock ............................................................................ 12
1.4.1. Ni dung c bn ca phng php Hartree- Fock ................................... 12
1.4.2. Nng lng ............................................................................................. 15
1.4.2.1. Nng lng orbital. Cng thc Koopmans ........................................... 15
1.4.2.2. Nng lng nguyn t, phn t............................................................ 15
1.5. Cc phng php sau Hartree-Fock ............................................................... 15
1.6. B hm c s- Basis Set ................................................................................ 18
1.6.1. B c s minimal STO-3G .................................................................. 18
1.6.2. B c s split-valance.......................................................................... 18
1.6.3. B c s polarizes ............................................................................... 19
1.6.4. B c s diffuse................................................................................... 19
1.6.5. B c s dunnings correlation consistent ............................................ 19
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 2

CHNG 2- L THUYT PHIM HM MT DENSITY FUNCTIONAL
THEORY .................................................................................................................. 20
2.1. Phng php phim hm mt ................................................................... 20
2.1.1. Mt trng thi ca electron ................................................................. 20
2.1.2. M hnh Thomas-Fermi .......................................................................... 21
2.1.3. Phng trnh Kohn-Sham ....................................................................... 22
2.2. Phim hm tng quan-trao i ..................................................................... 26
2.2.1. Xp x mt a phng Local Density Approximation (LDA) ......... 26
2.2.2. Xp x mt spin a phng Local Spin Density Approximation
(LSDA) ............................................................................................................... 28
2.2.3. Xp x gradient tng qut- Generalized Gradient Approximation ............ 30
2.3. Nhng b sung ca phng php phim hm mt ..................................... 35
CHNG 3- KHO ST GRAPHENE HU HN.............................................. 36
3.1. Gii thiu ...................................................................................................... 36
3.2. Cu to v tnh cht ca mng graphene ........................................................ 38
3.2.1. Cu to ca mng graphene .................................................................... 38
3.2.2. Tnh cht mng graphene ........................................................................ 40
3.3. Phng php tnh .......................................................................................... 42
3.4. Kt qu v tho lun ...................................................................................... 43
CHNG 4 KHO ST VT LIU (ZnO)
2
...................................................... 55
4.1. Cu hnh v trng thi h nhiu electron ........................................................ 55
4.2. Hng nguyn cu ........................................................................................ 56
4.3. Phng php tnh ton ................................................................................... 57
4.4. Kt qu v tho lun .................................................................................... 588
KT LUN ............................................................................................................... 63
TI LIU THAM KHO ........................................................................................ 64

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 3

LI CM N!
Con xin cm n ba m lun bn con, ng vin v gip cho trong nhng
lc con cm thy kh khn v b tc. Tnh yu thng ca ba m l s ng vin ln
nht i vi con. Con cm n ba m tht nhiu.
Em xin cm n cc thy c b mn Vt liu v linh kin mng mng khoa Khoa
hc vt liu to mi trng cho em hc tp v nghin cu, hon thnh kha lun tt
nghip ng tin .
Em chn thnh cm n thy TS. L Minh Hng, thy tn tnh hng dn em
trong thi gian thc hin ti. Nhng chia s v hng dn ca thy gip em hiu
hn cng vic ang thc hin v c mt nh hng r rng trn con ng sau ny.
Em cm n TTTO, TANT, TGST, TTBB, TLCT ng vin v gp chn
thnh gip em vt qua nhng giai on kh khn.
Cm n nhng ngi bn trong nhm G8 ca ti. Tuy mi trng lm vic ca
mi ngi khc nhau nhng chnh nhng li ng vin, nhng lc sn sng lng nghe
ca cc bn l mt ng lc gip ti lun hng v pha trc v quyt tm hn. Ti
s nh mi cc bn.
Cm n nhng ngi anh, ngi ch, nhng ngi bn lun yu qu v bn
cnh ng h ti.
Ti xin chn thnh cm n tt c. Chc nhng ngi ti yu qu nhiu sc khe
v thnh cng!

Tp. H Ch Minh, thng 7 nm 2011
Trn Nguyn


Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 4

DANH MC CC K HIU V CH VIT TT

HF - Hartree Fock
H - Hamiltonian
SCF - Self-Consider Field
CI - Configuration Interaction
CIS - Configuration Interaction with singles
CISD - Configuration Interaction with Single and Double
CISDT - Configuration Interaction with Singles Double and Triple
CC - Couple Cluster
MP - Moller Plesset
MO - Moleculer Orbital
STO - Slater Type Orbital
GTO - Gauss Type Orbital
DFT - Density Functional Theory
KS - Kohn-Sham
XC - Exchange- correlation
LDA - Local Density Approximation
LSDA - Local Spin Density Approximation
GEA - Generalized Expansion Approximation
GGA - Generalized Gradient Approximation




Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 5

DANH MC CC BNG

Bng 3.1- Khong cch C-C ca mu graphene C
24
H
12
c ti u bng phng
php B3LYP v PBEPBE .......................................................................................45
Bng 3.2- Gc lin kt gia C vi 2 nguyn t k cn ca mu graphene C
24
H
12
kho
st bng phng php B3LYP v PBEPBE ............................................................46
Bng 3.3- Gi tr nng lng thu c khi co gin khong cch ti v tr carbon khc
nhau. ......................................................................................................................51

DANH MC CC HNH V TH

Hnh 3.1- Mt s dng th hnh ca carbon (a) Fullerence; (b) Nanocarbon tube; (c)
Graphite .................................................................................................................37
Hnh 3.2- Graphene l mng li t ong hai chiu ca carbon ................................39
Hnh 3.3- mng c s ca graphene (a) v mng o ca n (b) .........................40
Hnh 3.4- Mu graphene C
24
H
12
c ti u ha bng phng php B3LYP ....44
Hnh 3.5- Ph dao ng ca graphene kho st bng phng php PBEPBE v B3LYP
...............................................................................................................................47
Hnh 3.6- Carbon trong mu kho st ti v tr 24 v 25 ..........................................48
Hnh 3.7- S thay i khong cch gia 2 nguyn t carbon ti v tr 24 v 25 .......49
Hnh 3.8- Carbon trong mu kho st ti v tr 7 v 25 ............................................49
Hnh 3.9- S thay i khong cch gia 2 nguyn t carbon ti v tr 7 v 25 .........50
Hnh 3.10- Carbon trong mu kho st ti v tr 7 v 10 ..........................................50
Hnh 3.11- S thay i khong cch gia 2 nguyn t carbon ti v tr 7 v 10 .......51
Hnh 3.12- Graphene pha tp N ti v tr C9-N36[5] ...............................................53
Hnh 3.13- Graphene pha tp N ti v tr C4-N36[5] ...............................................53
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

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Hnh 3.14- Graphene pha tp N ti v tr C5-N35[5] ...............................................53
Hnh 3.15- Nng lng co gin trong trng hp graphene tinh khit v pha tp nito
...............................................................................................................................54
Hnh 4.16- Cu hnh (ZnO)
n
c kho st .............................................................57
Hnh 4.17- Biu nng lng hnh thnh (ZnO)
2
trong ba trng thi spin khc nhau
...............................................................................................................................58
Hnh 4.18- Cu hnh (ZnO)
2
trng thi singlet .....................................................59
Hnh 4.19- Cu hnh (ZnO)
2
trng thi triplet ......................................................59
Hnh 4.20- Cu hnh (ZnO)
2
trng thi pentet ......................................................59
Hnh 4.21- Mu phn t (ZnO)
2
c ti u ha bng chng trnh Gaussian 03W
...............................................................................................................................60
Hnh 4.22- Nng lng ca h (ZnO)
2
tng ng vi s thay i cu hnh trong ba
trng thi spin .........................................................................................................61













Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 7

LI M U

Khi ra i c hc lng t 1926 n nay, lch s c hc lng t l mt chui
di nhng c gng ca nhiu nh khoa hc trong hu ht cc lnh vc (ton hc, vt l,
ha hc, tin hc ) nhm tm cch gii gn ng phng trnh Schro dinger xy
dng hm sng cho h phn t. Vic gii chnh xc hm sng cho h phn t c mt
ngha quan trng trong vic cung cp y thng tin v mt nng lng ca h phn
t mi trng thi electron. Tuy nhin, vic tm ra li gii chnh xc cho phng trnh
Schro dinger l mt vic ht sc kh khn bi s tng tc gia cc ht (ht nhn,
electron) dn n mt biu thc tch phn phc tp. Do vy cn c nhng phng php
tnh thch hp gii mt cch gn ng phng trnh Schro dinger cho h phn t.
Phng php nn tng gii phng trnh Schro dinger l l thuyt Hartree-
Fock, tuy nhin v c nhng mt hn ch nn phng php ny kt qu thu c cng
cha tht s ph hp vi thc nghim. L thuyt phim hm mt (Density
Functional Theory-DFT) ra i nh du mt bc tin mi trong lnh vc tnh ton
m phng. L thuyt phim hm mt bao hm mt lng ln cc phng php tnh
ton c s dng tnh nng lng tng cng ca h phn t, nguyn t bng cch
s dng mt phim hm nng lng ca mt electron v v tr cc nguyn t .
Khi l thuyt u tin ca Thomas- Fermi c thit lp t nhng nm 1920 th
vn cha c mt c s no c to ra lm nn tng cho mt l thuyt chnh xc ti
thi im by gi. n 1960, Hohenberg, Kohn v Sham gii thiu mt phng php
quan trng tnh ton nng lng tng quan trao i ca h cc ht l phng
php xp x mt a phng (Local Density Aproximation- LDA). S thnh cng
ca LDA cng vi kh nng tnh ton rt nhanh ca cng ngh my tnh hin i to
nn ng dng ph bin ca DFT.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 8

S pht trin nhanh chng ca cc thut ton chnh xc v hn th l s ci tin
v l thuyt, lm cho DFT tr thnh phng php trung tm ca vt l cht rn khi
nghin cu h c kch c t mt vi n hng trm nguyn t.
Khoa hc v cng ngh ngy mt pht trin, v ang thu v nhng thnh tu
ng khch l. Khoa hc my tnh c vn dng vo vi nhng phng php tnh
ngy cng c ci thin t c chnh xc ng tin cy v gn hn vi cc gi
tr thc nghim. S pht trin ca cc phn mm my tnh phc v cho vic tnh ton
gip cho vic nghin cu c m rng hn.
L thuyt lng t m ra mt chn tri mi cho vic nghin cu nhng cu
trc ni ti ca cc cht, c bit l nhng h cht phc tp cha n hng trm nguyn
t. i tng nghin cu c chn trong lun vn l vt liu graphene v vt liu
ZnO v nhng tnh cht v kh nng ng dng trong cc thit b v linh kin in t.
T lu ZnO c bit n v nghin cu v nhng c tnh rt qu bu nh :
rng vng cm rng (3.37 eV), nng lng lin kt exciton ln khong 60MeV
nhit phng, c tnh p in,c bit l khi n cu trc nano. Chnh nh nhng
c tnh ny m ZnO rt thch hp ng dng trong cc thit b in t v quang in
t
Bn cnh nhng vt liu mi ngy mt c ci thin v tnh cht, th graphene
tuy ch mi c pht hin trong thi gian gn y nhng graphene li mang nhng
tnh cht l th vt tri hn nhng vt liu khc. c im thu ht cc nh khoa hc
nghin cu v graphene l nhng ming graphene ny c b dy ch bng mt nguyn
t v cu trc bn vng nhit thng. Hn na, cc electron i qua graphene hu
nh gp in tr rt t nn t sinh nhit. Graphene cng l mt cht dn nhit, nhit i
qua v pht tn rt nhanh. Mt khi c th iu khin tnh cht cng nh ch to nhng
ming graphene p dng vo din rng th gii hn kch thc nano khng cn l
mt mi bn tm ln i vi cc nh nghin cu.

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 9

PHN 1- L THUYT M PHNG
CHNG 1- C S L THUYT LNG T V L
THUYT HARTREE FOCK

1.1 Php gn ng Born- Oppenheimer
n gin ha li gii cho phng trnh Schro dinger, ngi ta da trn mt
thc t l: do khi lng ht nhn ln hn rt nhiu so vi khi lng ca cc electron
nn cc ht nhn chuyn ng chm hn rt nhiu so vi electron (iu ny cng chnh
xc vi cc cht rn, khi m cc ion dng ch yu nh x cc nt mng c nh,
hoc di chuyn nhng rt t). Nh vy, chng ta c th coi nh electron c di chuyn
trong mt trng c to t ht nhn c nh. Phng php xp x nh vy gi l
phng php gn ng Born-Oppenheimer.
Trong phng php Born-Oppenheimer, khi ht nhn c gi c nh th ng
nng ca cc ht bng khng v th nng ca chng n thun ch l hng s.
Nh vy, Hamiltonian lc ny ca h c th vit ngn gn nh sau :
E
cIcc
=
1
2

2

z
A
|
i
-R
A
|
+
1
|
i
-
]
|
N
]>1
N
=1
M
A=1
N
=1
N
=1
(1.1)
= I + u + I
Trong :
I =
1
2

2 N
=1
l ton t ng nng
u =
z
A
|
i
-R
A
|
= :(r

)
N
=1
M
A=1
N
=1
l ton t tng tc electron-ht nhn
I =
1
|
i
-
]
|
N
]>1
N
=1
l ton t tng tc electron-electron
Trong biu thc ca U ta t :
:(r

) =
z
A
|
i
-R
A
|
M
A=1
(1.2)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 10

v gi l th nng tc dng ln electron th i th ny gy ra bi ht nhn.
Trong cch vit Hamiltonian ta s dng h n v di l bn knh Bohr,
n v in tch l in tch electron, n v khi lng l khi lng electron.
Vic gii phng trnh Schro dinger vi Hamiltonian (1.1) s tm c hm sng
in t
cIcc
v nng lng in t E
cIcc
. Nng lng tng cng ca h thc ny l
tng ca E
cIcc
v nng lng tng tc ca ht nhn E
nuc
:
E
totuI
= E
cIcc
+ E
nuc
(1.3)
y,
E
nuc
=
z
A
z
B
|R
A
-R
B
|
M
B>A
M
A=1
(1.4 )
1.2. Nguyn l Pauli
Pauli pht hin tnh cht ca hm sng ca cc ht vi m nh sau :
Hm sng ca h gm cc ht fermion (c gi tr m
s
= n +
1
2
, n l s nguyn)
c tnh bt i xng:
(r
1
, r
2
, r

, r
]
, . . , r
N
) = (r
1
, r
2
, r

, r
]
, . . , r
N
) (1.5)
Hm sng ca h gm cc ht bosson (c gi tr m
s
= n, n l s nguyn) c tnh
i xng:
(r
1
, r
2
, r

, r
]
, . . , r
N
) = (r
1
, r
2
, r

, r
]
, . . , r
N
) (1.6)
Electron thuc cc ht fermion. Hm sng ca electron do phi c tnh bt
i xng.
1.3. Phng php Hartree
Hartree l ngi t nhng vin gch u tin trn con ng tm cch gii
phng trnh Schro dinger cho h thng nhiu electron. ng ngh xy dng hm
sng bng tch ca cc hm sng mt electron:
(r
1
, r
2
, . . , r
N
) = c
1
(1)c
1
(2) c
1
(N) (1.7)
Trong c
1
(i) l hm sng ca electron th i . Tuy nhin:
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 11

- Hm sng c xy dng nh trn l mt hm i xng v vi phm
nguyn l bt i xng ca Pauli khi p dng cho electron l ht thuc loi
fermion.
- Mc khc, bn cht ca electron trong nguyn t l khng th phn bit
c nn khng th gn mt hm sng mt electron xc nh c
1
cho mt
electron xc nh (i).
gii quyt vn ny, Slater biu din hm ca mt h gm n electron
bng mt tch bt i xng ca cc hm sng mt electron c
1
(i) dng nh thc nh
sau :
(1.8)
nh thc trn c gi l nh thc Slater. Gi tr
1
N!
l h s chun ha
bo m iu kin chun ha ca hm sng .
Hm sng mt electron c

(i) l hm sng mt electron c tnh n trng thi


spin ca electron v c gi l hm spin orbital:
c(i) = (r

). o(s), o = o, [ (1.9)
Hm o(s), [(s) l hm spin m t trng thi spin electron, chng l cc hm
trc giao. Hm (r

) l hm sng khng gian. thun tin tnh ton cc hm


c(i) cng c chn l trc giao.
Theo tnh cht ca nh thc khi trt t ca hai hng hoc hai ct trao i cho
nhau nh thc s i du nn hm sng biu din dng nh thc Slater tun theo
nguyn l bt i xng ca Pauli.
V tt c electron u c th c mt trong tt c cc orbital nn yu cu v vn
cc electron l khng th phn bit c tho mn. Khi hai hng hoc hai ct
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 12

ging nhau th gi tr ca nh thc bng khng do s khng c hai spin orbital hon
ton ging nhau tc l khng c hai electron c cng bn s lng t (nguyn l loi
tr Pauli).
1.4. Phng php Hartree-Fock
Phng php Hartree-Fock l phng php gii phng trnh Schro dinger
trn my tnh. T c s ca phng php ny, ngi ta xy dng nn nhng phng
php phc tp hn c chnh xc cao, ng thi pht trin cc phng php gn ng
n gin hn p dng tnh ton cho cc h thng phn t ln.
1.4.1. Ni dung c bn ca phng php Hartree-Fock
Phng php HF p dng tng ca Hartree nhng hm sng c xy dng
theo nh thc Slater.
T E = E (1.10)
Nhn mi v vi hm v ly tch phn trn ton b khng gian:
E

J: = E J: (1.11)
Do iu kin chun ha ca hm sng J: = 1 v :
E = E

J: (1.12)
n gin, dng tch phn c vit gn nh sau :
E = |I + u +I | (1.13)
Biu din hm sng di dng h thc Slater ta c :
E = (
S
|E

|
S
) =

+
1
2
([
]
K
]
)
N
]=1
N
=1
N
=1
(1.14)
Trong :

= (c

|
`
|c

(i)) = c

(i) ]
1
2

2

z
A

iA
M
A
c

(i)Jr

(1.15)
[
]
= [c

[
`

c
]
(]) = c

(i)c

(i)
1

i]
c
]
(])c
]
(]) Jr

Jr
]
(1.16)
K
]
= [c

(i)K

c
]
(]) = c

(i)c
]
(i)
1

i]
c
]
(])c
]
(]) Jr

Jr
]
(1.17)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 13

[
]
c gi l tch phn Coulomb th hin lc y gia hai electron i v j . K
]

l tch phn trao i khng c ngha vt l. S xut hin ca K
]
l h qu ca tnh
cht bt i xng ca hm sng. Do cc hm spin o(s)v [(s) trc giao
(o(s)|[(s)=0) nn tch phn K
]
ch xut hin i vi electron c cng spin. [
`
: K


c gi l ton t Coulomb v ton t trao i nng lng.
Da theo nguyn l bin phn ngi ta s tm cc hm c

sao cho gi tr nng


lng E l cc tiu. lm vic ny cn p dng phng php Lagrange vi iu kin
l cc hm c

trc chun s tm c mt h phng trnh m t iu kin c gi tr


nng lng cc tiu gi l phng trnh Hartree - Fock :

, (i = 1,2,S , N) (1.18)
Trong : e

l h s Lagrange c ngha vt l nh l nng lng ca cc


orbital phn t c

(orbital mt electron).
`
c gi l ton t Fock v c dng nh sau

=
1
2

2

z
A

iA
+ I
HP
(i) =
M
A

+ I
HP
(i) (1.19)
I
HP
(i) c gi l th nng Hartree-Fock. N din t lc y trung bnh m
electron i phi chu t tt c cc electron cn li:
I
HP
(i) = ([
`

(i) K

(i))
N

(1.20)
I
HP
(i) ch c th xc nh khi bit cc hm sng mt electron c

, trong khi
cc hm ny li l cc hm phi i tm, do h phng trnh Fock phi c gii
bng phng php lp gi l Trng t hp SCF (Self-Consider Field). Nguyn tc
ca SCF gm cc bc sau :
(i) D on cc hm spin orbtal, t tnh I
HP
(i)
(ii) Gii phng trnh HF, thu c mt b cc spin orbital mi
(iii) Lp li vic tnh I
HP
(i) v gii phng trnh HF cho n khi I
HP
(i)
v cc spin orbital khng thay i na.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 14

Vn n y, vn cha c gii quyt xong. Vic tm cc hm spin tha
mn phng trnh Hartree Fock ch lm c trn cc nguyn t bng phng php s
l mt phng php khng c tnh h thng v khng th p dng trong my tnh.
Roothaan-Hall ngh khai trin phn khng gian ca hm sng dng t hp
tuyn tnh ca mt b c s gm K hm |
u
| bit. (Tch phn ca hm spin orbital
s c mt s bng khng do s trc giao ca hm spin, s cn li th bng chnh tch
phn ca hm khng gian):

= c

(1.21)
Phng trnh Hartree-Fock tr thnh :

`
c

= e

(1.22)
Nhn mi v vi hm

v ly tch phn c hai v :


c

`
(1)Jr = c

(1)

(1)Jr

(1.23)
F

= e

C
v
(1.24)
Vi F

(1)
`
(1)

(1)Jr v S

=
u

Jr (1.25)
Phng trnh trn c gi l phng trnh Roothaan-Hall. Rt gn dng ma
trn nh sau :
FC = SCe (1.26)
Nh phng php trin khai ca Roothaan-Hall m vic tm hm sng c

tr
thnh vic tm cc h s c

. Gii phng trnh s thu c 2K hm spin orbital. K hm


spin orbital ng vi o spin v K hm spin ng vi [ spin.
S hm c s K cng ln th linh ng khi trin khai hm spin orbital cng
ln, gi tr E thu c cng nh v do mc chnh xc cng tng.




Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 15

1.4.2. Nng lng
1.4.2.1. Nng lng orbital. Cng thc Koopmans
Gi tr ny thc cht l h s Lagrange, tuy nhin do phng trnh Fock c dng
nh phng trnh Schro dinger
`
c

= e

, nn ngi ta gn cho n ngha l nng


lng orbital c

. Lu rng tng cc nng lng e

khng bng tng nng lng E


e

= < c

|
`
|c

> =

+ ([
]
K
]
N
]
) (1.27)
Koopmans chng minh mt cch gn ng c th xem e

bng nng lng ion


ha dng bc mt electron nm orbital th i ra khi phn t.
1.4.2.2. Nng lng nguyn t, phn t
Nng lng E ca nguyn t hoc phn t c xc nh bng cng thc (1.15)
cng vi nng lng tng tc ca cc ht nhn vi nhau:
E
HP
=

+
1
2
N
=1
([
]
K
]
)
N
]=1
N
=1
+ I
NN
(1.28)
V
e

+
N

([
]
K
]
)
N
]
N

(1.29)
Nn
E
HP
=

1
2
N
=1
([
]
K
]
)
N
]
N

+ I
NN
(1.30)
n v ca nng lng tnh theo n v nguyn t l Hartree (1 hartree =
627.509 kcal/mol). Gi tr nng lng theo qui c tnh bng khng khi cc ht nhn
v electron hon ton tch xa nhau. Khi kt hp thnh phn t nng lng ca h s
gim xung. Do , gi tr ca nng lng s nh hn 0.
1.5. Cc phng php sau Hartree-Fock
Nhc im ca phng php HF l x l cha y s tng tc gia cc
electron ang chuyn ng. S dng mt nh thc Slater, phng php HF ch tnh
c tng tc gia cc electron cng spin nhng b qua s tng tc gia electron
ngc spin. Trong thc t electron s di chuyn t trnh nhau linh ng hn v do
nng lng s thp hn tnh t HF.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 16

S khc bit gia nng lng c tnh t phng php HF s dng mt b c
s y v nng lng chnh xc thc t ca h ( trng thi c bn khng tng i
tnh gn ng Born-Oppenheimer) c gi l nng lng tng quan:
E
tq
= E
cx
E
HP
(1.31)
Nhc im th hai ca phng php ny l khng tnh ton c trng thi
kch thch ngoi tr trng hp trng thi kch thch c cu trc electron hoc cu hnh
hon ton khc vi trng thi c bn. Ngoi ra phng php HF cng khng th m t
chnh xc cc phn t trng thi chuyn tip, khi m cc lin kt ang sp t v h
thng ang trng thi trung gian gia v ng v v m.
Nhng phng php sau HF c th gii quyt c nhng vn v nng lng
tng quan ca hm sng va nu trn.
Phng php Moller Plesset
Phng php Moller Plesset hay phng php nhiu lon bt ngun t bi ton
thin vn, tnh qu o ca cc hnh tinh. Trong ho hc lng t, c th gii thch
chnh xc cc bi ton th thng thng ngi ta phi b qua cc thnh phn nh trong
ton t Hamiltonian. Sau s tnh gn ng cc hiu chnh cn thit bng mt
phng php l phng php nhiu lon. L thuyt nhiu lon c p dng cho
hai loi bi ton: bi ton dng v bi ton khng dng.
Xt l thuyt nhiu lon cho bi ton dng khng suy bin. Phng trnh
Schrdinger l:
E

n
=E
n
(1.32)
Theo gi thit, vi E

0
l ton t Hamiltonian ca bi ton no c gii,
gi l ton t khng nhiu lon, th E

ch khc vi E

0
rt t nn ta c th vit:
E

= E

0
+ zw (1.33)
Vi W l ton t nhiu lon, l mt hng s rt b. Thay (1.32) vo (1.33) ta
c :
(E

0
+ zw)
n
= E
n

n
(1.34)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 17

Gi s phng trnh tr ring E

n
0
= E
n
0
.
n
0
(1.35) c th gii chnh xc
c, t ta s tm c
n
0
v E
n
0
. Gi tr ca n c gi l s gn ng cp 0.
Nu z=0, th (1.34) bin thnh (1.35) gi s vi cc gi tr z nh, cc nghim
ca phng trnh (1.34) rt gn vi cc nghim ca (1.35), ngha l nh hng ca
nhiu lon phi lm thay i rt t cc gi tr ring E
n
0
v cc hm ring
n
0
khng
nhiu lon.
Khi khai trin hm ring v tr ring ca E

thnh chui ly tha:

n
=
n
0
+ z
n
(1)
+ z
2

n
(2)
+ = z
k

n
(k)
k=0
(1.36)
E
n
= E
n
0
+ zE
n
(1)
+ z
2
E
n
(2)
+ = z
k
E
n
(k)
k=0
(1.37)
Trong ,
n
(k)
v E
n
(k)
l cc hiu chnh b v hm sng v nng lng cp k tng
ng (cp 1, cp 2). Thay (1.36) v (1.37) vo (1.34) v bin i ta thu c
E

n
0
= z(w
n
0
+ E

n
1
) +z
2
(w
n
1
+E

n
2
) + = z(E
n
(1)

n
0
+ E
n
(0)

n
1
) +
z
2
(E
n
(2)

n
0
+ E
n
(1)

n
1
+ E
n
(0)

n
2
) +
(1.38)
tha mn vi mi , ta c h phng trnh :
E

n
0
= E
n
0
.
n
0
(1.39)
w
n
0
+ E

n
1
= E
n
(1)

n
0
+E
n
(0)

n
1
(1.40)
w
n
1
+E

n
2
= E
n
(2)

n
0
+ E
n
(1)

n
1
+E
n
(0)

n
2
(1.41)
Gii h phng trnh trn ta s thu c
n
(1)
, E
n
(1)
(trong s gn ng cp 1),

n
(2)
, E
n
(2)
(trong s gn ng cp 2). C th tip tc nh vy trong s gn ng cp
cao hn. Tuy nhin trong thc t ch cn n hiu chnh cp 1, cp 2 v nng lng l
.
Trong trng hp bi ton nhiu lon dng c suy bin bc k, v bn cht k
hm khng trc giao, ta cn trc giao ha chng bng cch t hp tuyn tnh k hm

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 18

Khi c suy bin, cha p dng nhiu lon th E
0
n
suy bin k ln, p dng nhiu
lon th E
0
n
b tch thnh k mc con gn nhau, m mi mc con c tnh theo nh
lut gn ng bc nht v c hm sng :
n
= C
n
.
n
o
n

c th gii h c suy bin bng phng php nhiu lon, dng cc php tnh
thch hp ta lm gim hoc trit tiu bc suy bin tnh nng lng. Hin nay,
phng php tnh rt mnh c dng l thuyt nhiu lon l MP
n
(Moller-Plesset bc n).
Vai tr ca phng php l nng cao chnh xc khi gii h lng t cho cc h phc
tp.
Ngoi phng php nhiu lon c trnh by trn, cc phng php sau
Hartree Fock cn c phng php tng tc cu hnh (Configuration Interation-CI) v
phng php Couple Cluster (CC).
1.6. B hm c s- Basis Set
B hm c s l mt s biu din ton hc ca cc orbital trong h.
1.6.1. B c s minimal STO-3G
STO3G l vit tt t Slater Type Obital, mi hm c xy dng t ba hm
Gauss. B c s ny l b c s ti thiu khng th nh hn c na. STO3G ch
gm mt hm (1s) cho cc nguyn t chu k 1 (He, H), 5 hm cho nguyn t chu k 2
(1s,2s,2p
x
, 2p
y
,2p
z
), 9 hm cho nguyn t chu k 3 (1s,2s,2p
x
, 2p
y
,2p
z,
3s,3p
x
, 3p
y
, 3p
z
).
1.6.2. B c s split-valance
B hm c s tch ha tr thng dng l 3-21G v 6-31G. Trong b hm c s
ny cc orbital ca lp bn trong v orbital ha tr c biu din khc nhau. Orbital
lp trong biu din bng mt hm do ba hoc su hm Gauss t hp li, cc orbital ha
tr c biu din tch ra thnh hai hm; mt do hai hoc ba hm Gauss t hp, mt
ch bao gm mt hm Gauss duy nht. B c s split valence cho kt qu tt hn hn
b hm c s nh nht. V d b hm c bn 3-21G ca hydro gm hai hm 1s, b
hm c bn 3-21G ca carbon gm mt hm 1s (orbital lp trong), hai hm 2s v su
hm 2p (orbital ha tr), tng cng chn hm, cho CH
4
tng cng c mi by hm c
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 19

s. tng chnh xc, cc orbital ha tr trong b hm c s c th c biu din
tch ra thnh ba hm, v d nh hm 6-311G.
1.6.3. B c s polarizes
Di tc ng ca cc ht nhn khc trong phn t, cc orbital s, p thc t s
khng hon ton cn i xng nh orbital ca nguyn t hydro. m t c s
khng i xng ny, cc hm p s c thm vo xy dng orbital ca nguyn t
hydro, cc hm kiu d, f s c thm vo cho cc nguyn t khc. V d: 6-31G(d),
6-31G(d,p) hoc 6-311G(2df,p), 6-311G(3df,2p),... B hm c s ny ch lm thay i
kch thc ch khng lm thay i hnh dng orbital.
1.6.4. B c s diffuse
m t hm sng ca cc ion m hoc ca cc phn t ln c cc electron
nm xa bn ngoi ht nhn, ngi ta a thm vo cc hm khuch tn, thng thng
l nhng hm Gauss c s m nh. V d 6-311+ G l thm mt b cc hm khuch
kiu orbital s v p cho cc nguyn t chu k II v III (Li Cl ). 6-311++G l thm mt
hm khuch tn s v p cho cc nguyn t chu k II, III v mt hm khuch tn s cho
hydro.
1.6.5. B c s dunnings correlation consistent
Cc b hm c s ny c thit k c bit cho cc php tnh chnh xc cao, c
s dng cc phng php x l tng tc ca electron. Chng bao gm bn b nh
valence double zeta (cc-pVDZ), valence triple zeta (cc-pVTZ), valence quadruple-zeta
(cc-pVQZ) v valence quintuple zeta (cc-pV5Z). Mt hm khuych tn ca cc loi s,
p, d, f,c th c thm vo nh aug-cc-pVnZ, (n=D, T, Q).





Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 20

CHNG 2- L THUYT PHIM HM MT
DENSITY FUNCTIONAL THEORY

2.1. Phng php phim hm mt
Phng php HF cho kt qu rt tt i vi di lin kt trong cc nguyn t,
nhng nng lng lin kt nhn chung khng ph hp vi kt qu thu c t thc
nghim. i vi cht rn, phng php HF gp phi vn khi m t mt mng v
cng quan trng, l cu trc vng nng lng. Phng php DFT c pht minh
nghin cu cc hiu ng tng quan m khng s dng n phng php hm sng
qu gi. Trong DFT, nng lng khng c tm ra nh l tr ring ca hm sng, m
tm thng qua phim hm ca n i vi mt trng thi.
2.1.1. Mt trng thi ca electron
Trong h in t, s ht electron trn mt n v th tch trng thi cho trc
c gi l mt electron ca trng thi . Mt electron l i lng trung tm
trong phng php DFT. Trong c hc lng t, i lng ny c nh ngha nh
sau:
p(r
1
) = N|(x
1
, x
2
, x
N
)|
2
Jo
1
Jx
1
Jx
N
(2.1)
Trong : x

l ta electron th i. N bao gm ta thc r


i
trong khng
gian v spin ca electron o

. Trong (2.1) ta ly tng theo spin.


p(r) xc nh xc sut tm thy bt k N electron trong th tch nguyn t dr.
Mt vi tnh cht ca p(r):
- L mt hm khng m ca cc bin khng gian, b trit tiu dn khi tin ra
v cng, v tch phn trong ton b khng gian s cho ta ton b s electron.
p(r ) = u
p(r)Jr = N
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 21

- L mt i lng c th quan st v c th o bng thc nghim, chng hn
bng nhiu x tia X.
- Ti bt k v tr no ca nguyn t, gradient ca p(r) c im gin on v
c mt nh
lim

i
A0
|

+ 2Z
A
]p(r) = u
y Z l in tch ht nhn, p(r) l gi tr trung bnh trn mt cu bn knh r
ca p(r).
- p(r) s gim theo tim cn ca hm m khi ra xa tt c cc ht nhn :
p(r) = c
-22I||

Vi I l nng lng ion ha.
2.1.2. M hnh Thomas-Fermi
y l mt m hnh DFT u tin, n nh du mt s thay i trong vic gii
phng trnh Schro dinger. L thuyt ny cho php ngi ta thay th hm sng phc
tp ca h N electron bng mt i lng mi n gin hn trong vic gii phng
trnh Schro dinger, chnh l mt electron p(r).
M hnh ny c xut mt cch c lp bi L.H Thomas v E.Fermi vo
nm 1927, trc c l thuyt ca Hartree-Fock. iu m hai tc gi thy r l c th s
dng cc nghin cu thng k tnh ton s phn b ca cc electron trong mt
nguyn t. V cc cng thc tnh ton i vi mt electron c th c tm ra t
nhng gi thit ny.
Trong m hnh ca Thomas v Fermi, h ch ra rng c s tn ti ca mt
phim hm nng lng v tm ra mt biu thc cho ng nng da trn mt ca cc
electron p(r), trong mt h th c thnh cao v hn.
Phim hm ca ng nng c m t nh sau :
I
1P
|p] = C
P
p
S
3(r)Jr (2.2)
C
P
=
S
1u
(Sn
2
)
23

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SVTH: Trn Nguyn Trang 22

Khi biu thc (2.2) c s dng cng vi nng lng ht gia electron-ht
nhn v nng lng Hartree, ngi ta s thu c biu thc nng lng Thomas-Fermi
cho mt nguyn t da trn mt electron c lp:
E
1P
|p] = I
1P
|p] Z Jr
p()
|R-|
+
1
2
Jr
1
Jr
2
p(
1
)p(
2
)
|
1
-
2
|
(2.3)
y Z l in tch ht nhn, R l vector v tr ht nhn. Ch c mt ht nhn
tham gia vo trong phng trnh ny l bi v l thuyt Thomas- Fermi khng d on
c bt k mt lin kt phn t no. Nu mun s dng l thuyt Thomas-Fermi cho
phn t th phi c ci tin v sa cha.
c v s sa cha ci tin mu Thomas-Fermi c thc hin v tri qua rt
nhiu nm, nhng vic khc phc l rt kh. Gn ng Thomas-Fermi khng m t
c cu trc lp ca electron trong nguyn t, khng dn ti lin kt ha hc trong
phn tHn na, phn nng lng tng tc electron-electron (do bn cht lng t
ca chuyn ng) ng gp vo tng nng lng ca trng thi c bn l nng lng
trao i (exchange) v tng quan (correlation) u b loi b. iu ny lm cho l
thuyt Thomas-Fermi c nhn nhn nh mt mu qu n gin i vi tin on
nh lng trong vt l nguyn t, phn t hay vt l cht rn. Nhng khim khuyt
ny phn ln c khc phc trong phng trnh ca Kohn v Sham, lm nn thnh
cng ca l thuyt DFT.
2.1.3. Phng trnh Kohn-Sham
Nhng phng php trc l c s ca phng php phim hm mt
nhng cha ch ra c cch p dng vo h c th v cha a ra c mt phim
hm ph hp lin h gia nng lng v mt electron. Nm 1965, Kohn v Sham
xut mt cch thc xc lp phim hm ni trn, trc ht l tnh n ng
nng vi chnh xc tng i. xc nh phn ng nng ny, Kohn v Sham a
vo khi nim h quy chiu khng tng tc c xy dng t mt tp hp cc orbital
l cc hm mt electron. Phn sai s cng vi tng tc gia cc electron kh nh s
c xc nh bng mt phim hm xp x.
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SVTH: Trn Nguyn Trang 23

Orbital v h quy chiu khng tng tc
Vi m hnh h kh ng nht khng tng tc, Thomas- Fermi xy dng
trc tip cc phim hm ng nng v tng tc electron-electron nhng kt qu p
dng li khng ph hp vi thc t, khng m t c lin kt ha hc. Kohn v Sham
tm ra mt cch tip cn khc, l da vo hm sng v lin h vi cch tip cn
ca Hartree-Fock.
Gi s mt h electron khng tng tc, ta c th vit ton t Hamilton dng:
E

s
=
1
2

2
+ I
s
(r

)
N

(2.4)
V lin h vi phng php Hartree-Fock th nh thc Slater l hm sng chnh
xc. i vi h tng tc th th I
s
l th hiu dng a phng tng t nh th hiu
dng trong phng trnh HF.
Ta a vo hm sng dng nh thc Slater:

s
=
1
N!
_

1
(1)
2
(1)
N
(1)

1
(1)
2
(N)
N
(N)
_ (2.5)
Cc orbital

tha mn phng trnh:

`
KS

= e

(2.6)
Vi
`
KS
l ton t Kohn-Sham mt electron:

`
KS
=
1
2

2
+ I
s
(2.7)
p dng cho h thc l h tng tc ta phi tm c th hiu dng thch hp
tha mn iu kin tng cc bnh phng module hm sng phi bng mt trng
thi c bn ca h tng tc.
Phng trnh Kohn-Sham
Kohn-Sham ngh dng biu thc di y nhn c ng nng chnh xc
ca h khng tng tc c cng mt nh h thc c tng tc
I
s
=
1
2

|
2
|

(2.8)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 24

Tt nhin, ng nng ca h khng tng tc khng th bng ng nng h thc
c tng tc d chng c chung mt mt . Bao gm phn sai khc ny, Kohn-Sham
a vo s hng nng lng tng quan trao i E
xc

F|p(r)] = I
s
|p(r) +[|p(r)] + E
xc
|p(r)] (2.9)
Ngha l
E
xc
|p(r)] = (I|p(r)] I
s
|p(r) +(E
cc
|p(r)] [|p(r)]) = I
c
|p(r)] +K|p(r)]
(2.10)
T biu thc trn ta thy s hng nng lng tng quan trao i trong phng
php KS khng ng nht vi phn tng quan trao i trong phng php HF m n
bao gm c mt phn ng nng khng c xc nh chnh xc.
Vn t ra l lm th no xc nh duy nht cc orbital

trong h khng
tng tc hay ni cch khc l lm th no nh ngha c I
s
c th nhn c
nh thc Slater tng ng vi mt in tch ng nh h thc.
Ta vit li biu thc nng lng c s ph vo orbital :
E|p(r)] = I
s
|p(r)] + [|p(r)] + E
xc
|p(r)] + E
Nc
|p(r)]
= I
s
|p(r)] +
1
2

p(
1
)p(
2
)

1 2
Jr
1
Jr
2
+ E
xc
|p(r)] + p
0
(r)I
Nc
Jr =

1
2

|
2
|

+
1
2
|

(r
1
)|
2
1

1 2
|

(r
2
)|
2
Jr
1
Jr
2
+ E
xc
|p(r)]
N


z
A

A
|

(r)|
2
Jr
N

(2.11)
Trong biu thc trn s hng duy nht khng c dng ph thuc r rng l E
xc
.
p dng phng php bin phn vi iu kin rng buc : (

|
]
) = o
]
dn
n phng trnh :
_
1
2

2
+[
p(
2
)

1 2
Jr
2
+ I
xc
(r
1
)
z
A

A
M
A
_

= [
1
2

2
+ I
c]]
(r)

= e


(2.12)
Xem xt cc thnh phn trong th hiu dng KS:
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 25

I
s
(r) = I
c]]
(r) =
p(
2
)

1 2
Jr
2
+ I
xc
(r)
z
A

A
M
A
(2.13)
I
xc
(r) =
6L
xc
6p
(2.14)
V cha bit c dng ph thuc ca E
xc
nn cng cha bit c dng ca
I
xc
. Nu bit dng chnh xc ca E
xc
, phng trnh KS s cho ra ra tr ring chnh xc
nhng cho n nay phim hm ny mi ch c a ra mt cch gn ng. V s pht
trin ca l thuyt phim hm mt tp trung vo vic tm ra dng tt hn ca phim
hm tng quan trao i.
Khi c dng ca phim hm tng quan trao i th vic gii phng trnh
KS c thc hin bng cch gii lp tng t nh phng trnh HF.
Phim hm tng quan trao i phi c xc nh chung cho tt c cc h.
Nhiu dng phim hm tng quan trao i c a ra, vic xy dng cc dng
gn ng ny da vo so snh vi thc nghim hoc trn c s so snh vi mt
phng php hm sng mc cao. Thng thng phim hm c tch thnh 2 phn
ring r, phn tng quan v phn trao i:
E
xc
|p] = E
x
|p] + E
c
|p] = p(r)e
x
|p(r)]Jr +p(r)e
c
|p(r)]Jr (2.15)
e
x
v e
c
c a vo biu thc vi ngha l mt nng lng.
Th tng quan trao i tng ng c xc nh l o hm ca nng lng
theo mt :
I
xc
(r) =
6L
xc
|p]
6p()
= e
xc
|p(r)] + p(r)
s
xc
()
p
(2.16)
Tng quan gia cc electron c spin song song khc vi tng quan gia cc
electron c spin i song, nng lng trao i theo nh ngha ch lin quan n cc
electron c cng spin:
E
x
|p] = E
x
u
|p
u
] + E
x
[
|p
[
] (2.17)
E
c
|p] = E
c
uu
|p
u
] + E
c
[[
|p
[
] + E
c
u[
|p
u
, p
[
] (2.18)
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SVTH: Trn Nguyn Trang 26

Mt tng l tng ca phn ng gp ca cc electron o v p = p
u
+ p
[
.
Tuy nhin cc phim hm thng c vit theo phn cc ha spin v bn knh
ca th tch hiu dng cha mt electron r
s
=
p
o
- p

p
o
+ p

v r
s
= _
3
4np
3
(2.19)
C nhiu dng phim hm tng quan trao i c thit lp, mt s dng
thng dng nh BPW91, BLYP, B3LYP, B3PW91
2.2. Phim hm tng quan-trao i
2.2.1. Xp x mt a phng Local Density Approximation (LDA)
tnh n nhng tc ng trong trao i v tng quan (hon ton khng
c cp trong l thuyt ca Thomas-Fermi), phng php xp x mt a
phng (Local Density Approximation- LDA ) i vi phim hm tng quan v trao
i c gii thiu. Nguyn l ca s xp x ny l tnh ton nng lng XC trn
tng ht ca kh electron ng nht nh mt phim hm ca mt , e
x
(p(r)) v
e
c
(p(r)). Nhng hm ny sau c s dng nh nhng nh lng ca
nng lng XC trn mt ht ca h thng khng ng nht tng ng:
E
xc
LA
|p] = p(r)(e
x
(p) + e
c
(p))Jr (2.20)
Ngay lp tc chng ta s ngh rng s dng mt phim hm nh vy l ch ph
hp cho h thng c mt bin i chm, nhng LDA cho ta mt kt qu tt n
ngc nhin khi ng dng vo nhiu nghin cu cc h thng m mt bin i tng
i nhanh. S ni ting ca DFT hin i gn lin vi s thnh cng ca LDA.
Vo khong cui nhng nm 1920, u nm 1930, phng php LDA u tin
tnh ton nng lng trao i c gii thiu bi Dirac, trong nng lng trao
i-tng quan c xc nh nh sau:
E
x,uc
LA
|p] = C
x
p(r)
43
Jr (2.21)
y, C
x
l hng s :
C
x
=
3
4
. (
3
n
)
13
(2.22)
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SVTH: Trn Nguyn Trang 27

Phim hm ny c s dng cng vi m hnh ca Thomas-Fermi, v n c
gi l phng php Thomas-Fermi-Dirac, nhng n khng to ra c ci tin ng k
no i vi nhng sai xt trong vic ly xp x phim hm ng nng trong m hnh
Thomas-Fermi. Sau ny, mu Thomas-Fermi-Dirac-Weizscker bao gm nhng iu
chnh gradient i vi phim hm ng nng trong mu Thomas-Fermi ch ra nhng
ci tin ln i vi mu ny.
Nm 1951, Slater s dng mt phim hm trao i LDA thun tin trong
tnh ton s dng phng php Hartree-Fock, bi v n l s hng trao i, nn chi
phi hu ht thi gian ca tnh ton Hartree-Fock. Slater tnh ton th trao i
LDA thay v nng lng LDA .V thu c th trao i c dng:
I
x,SIutc
LA
|p] =
3
2
(
3
n
p(r))
13
(2.23)
S hng ny c s dng trong phng trnh Hartree-Fock thay v ton t trao
i Hartree-Fock phc tp cho chng ta mt phng php gi l phng php
Hartree-Fock-Slater (phng php HFS). Th trao i thu c t tnh ton ca
Slater khng ging vi th trao i thu c t vic ly o hm (2.23):
I
x,SIutc
LA
|p] = (
3
n
p(r))
13
(2.24)
S khc nhau ny bt ngun t vic s dng LDA i vi hoc l nng lng
trao i hoc l th trao i. S khng r rng ca th trao i dn ti s hu dng
ca phng php HFS cng vi mt thng s c th iu chnh, , t trc th trao
i. Ngy nay, phim hm trao i ca Dirac - c nhc n nh phim hm trao
i LDA, cho ta nng lng trao i chnh xc ca h ht ng nht. iu ny
c kt lun mc d th a ra bi Slater i vi cc orbital Kohn-Sham l tt hn.
Nhn chung, trong tt c cc tnh ton ca cc nguyn t khi khng ch n
nng lng tng quan, mt gi tr nm gia o = S2 (tng ng vi Dirac LDA) v
o = 1(tng ng vi Slater LDA) to ra kt qu tt hn c hai gi tr bin. Nhng
phim hm tng quan LDA u tin c cht lng kh ti. iu ny lin h vi
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 28

nhng vn thc hin khai trin nhiu lon h nhiu ht gii hn mt thp. Vn
ny khng c gii quyt cho n khi tm ra phim hm a phng ph thuc
vo spin.
2.2.2. Xp x mt spin a phng Local Spin Density
Approximation (LSDA)
Phng php LDA c gii thiu phn trn a n nhng kt qu chnh
xc cho kh electron ng nht b chnh spin, nu nh mt phim hm trao i-
tng quan chnh xc c s dng. i vi nhng m t cho nhng h thng c
t trong mt t trng ngoi, cc h thng b phn cc hoc nhng h thng c hiu
ng tng t l rt quan trng. Khi ny h thng Kohn-Sham b chnh spin v LDA
khng th p dng vo y c.
L thuyt Kohn-Sham phn cc spin c pht trin vo u nhng nm
1970, v mt thi gian ngn sau , ngi ta thy rng nhng hiu chnh tng i
chng hn nh cp spin qu o c th c bao hm trong hnh thc lun ny. Trong
l thuyt phn cc spin ca Kohn-Sham, cng vi phng php xp x mt spin a
phng (LocaSpin Density Approximation - LSDA), nng lng trao i tng tc c
dng nh sau:
E
xc
LSA
|p
u
, p
[
] = p(r)e
xc
(p
u
(r), p
[
(r))Jr (2.25)
y, p
u
, p
[
l mt spin up v spin down.
Nng lng tng quan-trao i trong phng php LSDA c th c vit
tng ng l:
E
xc
LSA
|p, V] = p(r)e
xc
(p(r), V(r)Jr) (2.26)
y:
p(r) = p
u
(r) +p
[
(r) v V(r) =
p
o
()- p

()
p()
(2.27)
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SVTH: Trn Nguyn Trang 29

l mt tng cng v mt phn cc spin tng ng. Trong nhng phng trnh
v l tng ng i din cho spin-up (hng ln) v spin-down (hng xung). Do
kh nng phn tch ca phim hm nng lng trao i:
E
x
|p
u
, p
[
] = E
x
|p
u
, u] + E
x
|u, p
[
] (2.28)
V spin c lp:
E
x
|p, u] = E
x
|u, p] (2.29)
Ta c th vit li dng ca nng lng trao i:
E
x
|p
u
, p
[
] =
1
2
E
x
|p
u
, p
u
] +
1
2
E
x
|p
[
, p
[
] (2.30)
Khi thay th phim hm nng lng trao i Dirac vo nhng phng trnh ,
v s dng mi quan h:
p
u
=
1
2
(1 +V)p, p
[
=
1
2
(1 V)p (2.31)
ta s thu c nng lng trao i ph thuc vo mt spin a phng trn mi ht
l:
e
x
(p, V) = e
x
(p, u) + (V)(e
x
(p, 1) e
x
(p, u) ) (2.32)
y:
(V) =
(1+V)
4 3
+(1-V)
4
3-2
2
4 3
-2
(2.33)
c gi l hm ni suy Von Barth-Hedin, v:
e
x
(p, u) = C
x
p
13
, e
x
(p, 1) = 2
13
C
x
p
13
(2.34)
Nng lng tng quan trn mt ht trong phng php LSDA rt kh thu c
ring r t nng lng trao i. iu ny c bit ng trong trng hp V u v
V 1. Khi xy dng LSDA, ngi ta thng gi s rng nng lng tng quan trao
i trn mt ht c th c ni suy cho h thng phn cc spin cc b, ging nh
nng lng trao i trn mt ht:
e
xc
(p, V) = e
xc
(p, u) + (V)(e
xc
(p, 1) e
xc
(p, u)) (2.35)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 30

y, (V) vn l hm ni suy nh trn. Trong gii hn mt cao, e
xc
(p, u),
c xp x bi l thuyt h nhiu ht cng vi vic ly tng trong ton khng gian v
e
xc
(p, 1) c cho bi h thc t l pha ngu nhin :
e
xc
RPA
= (p, 1) =
1
2
e
xc
RPA
(2
4
p, u) (2.36)
i vi mt thp v trung bnh, ngi ta s dng nhng iu chnh s i
vi cc kt qu Monte-Carlo lng t chnh xc.
2.2.3. Xp x gradient tng qut- Generalized Gradient Approximation
Vic khai trin theo gradient ca mt xut hin u tin trong nhng n bn
ca Hohenberg, Kohn v Sham. Phng php khai trin ny c bit n vi ci tn
Khai trin suy rng gn ng gradient (GEA - Gradient Expansion Approximation).
Mc ch ban u l m rng phng php LDA. GEA l mt chui cc khai trin
theo bc tng dn ca gradient mt . Dng bc nht ca GEA sau c thc thi
v chy th i vi h cc nguyn t v phn t, v kt qu thu c sai hon ton.
Ngun gc ca vn GEA sau ny c tm ra l do s vi phm cc quy tc ly
tng v iu kin khng r rng i vi trao i l trng - c hai u l nhng iu
kin vt l quan trng v u c p ng trong LDA. Mc d kt qu ca GEA l rt
tht vng nhng n cung cp nhng nn tng c bn cho phng php xp x
gradient tng qut (GGA - Generalized Gradient Approximation), mt phim hm
tng quan-trao i hin nay ang rt ph dng trong vt l cht rn. i vi mt gi
tr mt p(r) bt k, khng d g khi xc nh chnh xc gi tr nng lng trao i-
tng quan E
xc
|p] c. Tuy nhin, nu nh p(r) thay i tng i chm th ngi
ta c th vit :
E
xc
|p] = p(r)e
xc
(p(r)Jr (2.37)
y, e
xc
(p(r)) l nng lng trao i-tng quan trn mt ht ca h electron
ng nht c mt p.
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SVTH: Trn Nguyn Trang 31

Trong trng hp mt bin i chm, ta c th khai trin nng lng tng
quan-trao i nh sau:
E
xc
|p] = e
xc
|p]pJr + e
xc
(2)
|p]|p|
2
Jr +. (2.38)
y, e
xc
(2)
|p] l phn nng lng tng quan trao i ca s hng th hai trong
khai trin nng lng theo ton t gradient ca mt .
Trong khai trin (2.38), nu ch tnh n s hng u tin, ta c th nhn ra ngay
l nng lng trao i-tng quan trong LDA, hm ny ch ph thuc vo . Cn
nu xt thm n s hng th hai, ta s thy nng lng trao i-tng quan s ph
thuc vo 2 bin l p v p. Khi n c th c vit di dng:
E
xc
|p] = (p, p)Jr (2.39)
chnh l dng n gin nht ca phng php GGA c nh ngha t gia u tp
k 80. Trong phng php xp x ny, c s bao hm gradient nh l mt bin mi.
V sau ny, ngi ta c gng tm c nhng s tt nht c th m t
nng lng tng quan-trao i trong phng php GGA, chng hn nh thm vo
cc thng s v spin. Nhn chung, dng y (tng qut) ca nng lng trao i-
tng quan trong phng php GGA c dng:
E
xc
uuA
|p
u
, p
[
] = (p
u
, p
[
, p
u
, p
[
) Jr (2.40)
Nhng phng php GGA u tin cho nng lng trao i tng quan a
ra nhng ci tin ln i vi phng php LSDA. Phng php LSDA ch ra cc
tnh cht v mt cu trc v cc tnh cht dao ng tng i tt cho c cht rn v
phn t. Nhng i vi cc phn t, phng php LSDA c mt xu hng r rng i
vi lin kt ph linh ng. Sau khi phng php GGA c gii thiu, cc cng b v
phim hm nng lng trao i-tng quan da theo phng php ny tng nhanh
chng.
Nhng bc quan trng dn ti GGA phn ln c thc hin bi Perdew v
cc cng s. ng a ra mt th tc trong gii hn r rt trao i-tng tc l
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 32

trng GEA trong mt khng gian thc bng cch s dng hm Delta, hi phc quy
tc ly tng v cc iu kin l trng khng r rng. Theo , GGA c th c vit
thun tin da trn mt hm gii tch c bit n nh l mt tha s gia tng,
F
xc
|p(r), p(r)]. Hm ny sa cha trc tip nng lng LDA:
E
xc
uuA
|p(r)] = p(r)e
xc
hom
|p(r)]F
xc
|p(r), p(r)]Jr (2.41)
Thng th tha s gia tng trong GGA c vit da trn bn knh Seitz r
s
, v
s hng khng th nguyn s(r):
s(r) =
|p()|
2k
F
()p()
(2.42)
y k
P
l vector sng Fermi:
k
P
(r) = |Sn
2
p(r)]
1
3
(2.43)
V rng GGA khng phi l dng phim hm duy nht, v F
xc
|r
s
, s] theo s i
vi xc gi tr r
s
khc nhau s cho php mt cch hiu qu kim tra v so snh cc
dng GGA khc nhau.
Bng th tc gii hn khng gian thc, phng php GGA thnh cng trong
vic gii quyt hai li chnh trong GEA. N a ra nhiu ci tin hn LDA trong
mt vi trng hp c bit. Kt qu ng ch nht l s gim ng k li trong lin
kt ph ca LDA i vi cht rn v cc phn t. Tht cng bng m ni rng, s
thnh cng ca GGA i vi cc tnh cht phn t l nhn t chnh dn ti gii
thng Nobel ca Walter Kohn nm 1998.
Mt phim hm quan trng c s dng tri hn trong trng phi DFT cho
cht rn l PW91, c pht trin bi Perdew v Wang. N c xy dng theo li phi
kinh nghim bi v phim hm ny khng cha bt k mt tham s t do no c iu
chnh vi thc nghim. D nhin l n c xc nh t cc h thc c hc lng t
chnh xc. Trong phim hm PW91, tha s gia tng trao i c dng:

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 33

F
x
Pw91
|s] =
1 + u.1964Ss sinh
-1
(7.79S6s) +(u.274S u.1Su84c
-10 0 s
2
)
1 + u.1964Ss sinh
-1
(7.79S6s) + u.uu4s
4

(2.44)
y l mt s m rng i vi dng c a ra bi Becke (vi tn gi B88), mc d
n c v vu tun theo nhng iu kin chnh xc c thm vo chng hn nh
dng iu ng n trong gii hn bin i chm, mt vi biu thc t l, v cc gii
hn nng lng. Ta c th thy rng khng c s ph thuc ca tha s gia tng trao
i vo r
s
v rng nng lng trao i t l thun vi mt ng nht, v nh vy
dng ca F
x
(s) hu nh khng thay i i vi cc gi tr r
s
khc nhau. Phn ton hc
ca nng lng tng quan GGA l rt phc tp do cc h thc t l v nhng tng
tc khc nhau xy ra gia cc thnh phn spin ging nhau v khng ging nhau. Nng
lng tng quan c b chnh spin trong PW91 c th vit di dng:
E
c
Pw91
|p
u
, p
[
] = p(r)|e
c
(r
s
, V) +P(t, r
s
, V)]Jr (2.45)
y, e
c
(r
s
, V) l s tham s ha Perdew-Wang nng lng tng quan ca kh
electron ng nht, v t l mt s hng khng th nguyn c cho bi:
t =
|p()|
2gk
s
p()
(2.46)
y, k
s
= (4k
P
n)
12
, g = |[1 +V)
2
3
+ (1 V)
2
3
[ v V l bc phn cc spin.
Hm P = P
0
+ P
1
c nh ngha nh sau:
P
0
= g
3
[
2
2u
log |1 +
2u
[
t
2
+At
4
1+At
2
+A
2
t
4
] (2.47)
P
1
= :|C
c
(r
s
) C
c
(u)
3
7
C
x
]g
3
t
2
c
|-10 0 g
4
(k
s
2
k
F
2
)t
2
]
(2.48)
A = (2o[)(
1
c
-
2os
g
3

2
1) (2.49)
Vi o = u.u9, [ = :C(u), : = [
16
n
(Sn
2
)
1
3
= u.uu42SS, C
x
= u.uu1667
C
c
(r
s
) c xc nh bi:
C
c
(r
s
) = C
xc
(r
s
C
x
) (2.50)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 34

C
xc
(r
s
) = 1u
-3
2.5 6 8 +23 .26 6
s
+7.3 8 9 10
-3

s
2
1+8 .73 2
s
+0 .472
s
2
+7.3 8 910
-3

s
3
(2.51)
Nhng nghin cu sau ny khm ph ra rng, c mt vi bin ng phi vt l
trong th tng quan-trao i PW91 i vi gradient mt nh v ln. b p cho
s yu km ca phim hm PW91, phim hm PBE c xy dng . Hin nay, y
l phim hm c s dng ph bin nht ca phng php GGA. S khai trin chnh
xc n bc hai cho nhng bin i nh ca mt hoc s bin i chm c p
ng y bi PW91, nhng iu kin p buc ny c gim nh trong phim
hm PBE a ra mt s m t tt hn i vi cc h.
Trong phim hm PBE, hm F
x
(s) c dng n gin nh sau:
F
x
PBL
(s) = 1 + k
k
1+ s
2
k
(2.52)
Hng s p = u.219S1, k = u.8u4 c chn nh sau: khai trin gradient xung
quanh s=0 s cho ng c trng tuyn tnh chnh xc ca kh electron ng nht,
v phi tha mn bin a phng Lieb-Oxford:
p(r)e
x
PBL
(p(r), s(r)) 1.679p(r)
4
3
(2.53)
Phim hm PBE thng c xem nh mt phim hm nguyn l th nht, bi
v n c xy dng t nhng gii hn bit ca kh electron ng nht v nhng h
thc t l. Hn na, n khng cha bt k mt thng s no hoc l nhng hng s c
bn hoc c xc nh tha mn mt vi h thc c hc lng t xc nh.
Tuy nhin, cn ch rng, tr i nhng iu kin gradient cao v thp (ng
c trng tuyn tnh ca kh electron ng nht v bin Lieb-Oxford), hm trao i gia
tng l hon ton ty . iu ny dn n vic xy dng phim hm trao i
revPBE, n hu nh c cng tnh cht hnh thc chnh xc nh PBE, nhng ci tin
c nng lng nguyn t v nng lng bm ht ha hc. S quan tm u tin i
vi revPBE l khng m bo bin Lieb-Ofoxd. iu ny c bt buc trong phim
hm RPBE, phim hm ny ging nh ca revPBE, ci tin thm s m t cc phn
t, v ti thi gian ging nhau lp y bin a phng Lieb-Oxford.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 35

Sau ny, ngi ta ch ra rng mt vi tnh cht ca vt cht c tnh ton
cng vi phim hm RPBE v revPBE sai lch rt ln vi cc kt qu thc nghim,
v cn sai lch hn c phim hm PBE ban u. iu ny nh mt minh chng rng
nhng ci tin xa hn i vi nhng phim hm GGA ang tn ti phi xut pht t
vic la chn mt gii hn n gin hn ca dng phim hm hn l b b buc bi s
xp x gradient suy rng.
2.3. Nhng b sung ca phng php phim hm mt
Trong l thuyt phim hm mt , mt xch yu nht l i lng nng lng
trao i-tng tc cha c bit. Khi xem xt n kha cnh thc thi DFT trn mt
chng trnh my tnh, th s miu t cc orbital KS s ng vai tr chnh. Trong
chng trnh DACAPO, vic miu t cc orbital KS c thc hin bng cch s
dng cc gi th v sng phng. Cch tip cn ny cc k hiu qu cho cht rn v cc
hin tng b mt cng vi s tun hon lp li ca cc mng tinh th.












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SVTH: Trn Nguyn Trang 36

PHN 2- I TNG NGHIN CU V
PHNG PHP TNH
CHNG 3- KHO ST GRAPHENE HU HN

3.1. Gii thiu
Carbon l vt liu khi ngun cho s sng trn tri t, thnh phn c bn ca
tt c cc hp cht hu c. Do tnh linh ng ca carbon trong kh nng to thnh lin
kt, cc hp cht carbon a dng v hnh dng v tnh cht. Trong cc dng th hnh
ca carbon phi k n graphene, l mt n lp nguyn t carbon hai chiu c hnh
dng t ong, ng mt vai tr v cng quan trng trong vic to thnh cc dng th
hnh ca carbon. Tp hp nhiu lp carbon xp chng ln nhau s ti thnh vt liu
graphite. Mt tm graphene cun li s to thnh mt ng nano carbon mt chiu hay
to thnh qu cu khng chiu (Fullerene). Graphene l mt cht liu hon ton mi
n khng nhng mng nht m cn bn. L mt cht dn in, n dn in tt nh
ng. L mt cht dn nhit, n dn nhit tt hn mi cht liu bit khc. N hu
nh hon ton trong sut, nhng li m c ti mc ngay c helium, nguyn t nh
nht, cng khng th xuyn qua.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 37


Hnh 3.1 : Mt s dng th hnh ca carbon (a) Fullerene; (b) Nanocarbon
tube; (c) Graphite
Trc khi tm ra graphene, cc nh khoa hc nhiu ln tht bi khi c tch
nhng ming mng graphene t graphite. Ban u, ngi ta dng mt th thut ha
hc gi l chemical exfoliation tc l chn nhiu phn t ha hc vo gia nhng
phin graphene tch n ra. Tuy nhin ci m h c c ch l nhng mng by
nhy nh nh ni. T khng ai dng k thut ny ly graphene na. Sau , cc
nh khoa hc p dng mt k thut trc tip hn, gi l micromechanical cleavage
(ct vi c), tch graphite thnh nhng ming mng bng cch ch graphite vo mt mt
phng khc, t c th g nhng ming graphite vi dy khong 100 nguyn t.
Bng cch ny th nm 1990, cc nh vt l ngi c i hc RWTH Aachen
ly c nhng ming graphite mng n trong sut. Tuy nhin, cc thit b o thi
khng hin i gip ng nhn bit ra iu ny.
Khong 10 nm sau , khng c mt tin b no ng k. Mc d h c th
ly c nhng ming mng khong vi mi nguyn t, nhng ch l nhng
ming graphite mng, khng phi graphene. Lc , khng ai ngh graphene c th
hin din c trong thin nhin.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 38

Cho n nm 2004, Andre K. Geim v ng nghip ti i hc Manchester
Anh tnh c tm ra c mt cch mi to ra graphene. H dn nhng mnh vn
graphite trn mt ming bng keo, gp dnh n li, ri ko dt ra, tch ming graphite
lm i. H c lm nh vy nhiu ln cho n khi ming graphite tr nn tht mng,
sau dn ming bng keo ln silicon xp v ma st n. Vi ming graphite dnh trn
ming silicon xp, v nhng mnh thng c b dy l mt nguyn t. Mt ming
graphite dy mt nguyn t th khng th nhn thy c, nhng Geim thy c rng
mt ming graphite to ra mt cu vng nhiu sc mu rc r. n nay, quan st bng
knh hin vi, qua mu sc, cc nh nghin cu c th bit c dy ca ming
graphite. Mt ming graphite dy hn 100 lp (mu vng), dy 40 n 30 lp (mu
xanh dng), dy khong 10 lp (mu hng) hoc ch l 1 lp n chnh l graphene
(mu hng nht, hu nh khng thy c).
3.2. Cu to v tnh cht ca mng graphene
3.2.1. Cu to ca mng graphene
Graphene l mt n lp ca graphite, mng li t ong hai chiu ca cc
nguyn t carbon. l vt liu c nhng c im tuyt vi cn bng nhit nhit
ln hn 500 trong khng kh, tr vi hu ht cht kh, cng nh kim cng, c linh
ng cao v kh nng chu ti ln. Lin kt C-C trong tm graphene c di khong
0.142 nm. graphene, mi nguyn t carbon c ba mi lin kt cng ha tr nm cn
i trong mt phng, gc gia hai mi lin kt k nhau l 120
o
. Mi mi lin kt nh
vy li kt ni vi 1 nguyn t carbon ( cng ha tr) nn quanh mt nguyn t
cacbon c ba nguyn t carbon khc. Do , cc nguyn t trong graphene trng thi
lai ha sp
2
to thnh lin k bn vng v mt lin kt n to thnh vn o p
z
cn
li. Trong lin kt n u tham gia dn in v c nh hng quyt nh n tnh
cht t trng ca graphene.

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 39


Hnh 3.2: Graphene l mng li t ong hai chiu ca carbon
Mt vi thng s ca mng Graphene:
- Hng s mng : a=So
C-C
=2.46
- Vecto c s : o
1
= o(
3
2
;
1
2
) ; o
2
= o(
3
2
;
1
2
)
- Vector mng o: b
1

=
2n
u
[
1
3
; 1 ; b
2

=
2n
u
[
1
3
; 1
- C s: gm 2 nguyn t A: (0;0) v B : (
1
2
;
1
2
)
- Din tch ca n v A
c
= S
u
2
2
= u.uS1 nm
2
v mt nguyn t tng
ng l n
c
=
2
A
c
= S9 nm
2
= S9. 1u
15
cm
-2
.
- V s lng lin kt n bng s nguyn t carbon trong mt n v ca mng
nn mt cc lin kt n trong mng graphene l n
n
= n
C
= S9. 1u
15
cm
-2

n v ca mng Bravais c to bi 2 vector l o
1
v o
2
, mi cha 2
nguyn t A v B. T , ta v c vng Brillouin th nht c hnh lc gic (hnh
3.3). y ta ch n 4 im i xng I, M, K, K ; trong 2 im K v K l
khng hon ton i xng. Tuy nhin trong cc bi ton th ta c th coi hai im ny
l i xng, trong trng hp phi xt n bi ton c t trng ngoi, tng tc
spinth mi cn phn bit 2 im ny.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 40


a b
Hnh 3.3: mng c s ca graphene (a) v mng o ca n (b)
3.2.2. Tnh cht mng graphene
Graphene l vt liu mng nht trong tt c cc vt liu:
Graphene c b dy ch bng mt phn triu ca loi giy in bo thng thng
v bng 1/200000 si tc. Theo Geim, mt ngi khng th nhn thy mng graphene
v ch c knh hin vi in t ti tn nht mi nhn ra dy ny. Di knh hin vi,
mnh graphite dy gp 100 ln nguyn t carbon c mu vng, 30- 40 lp mu xanh
l, 10 lp c mu hng v graphene th mang mu hng rt nht, mt mng graphene
trong sut ch dy mt nguyn t.
Chuyn ng ca in t trong graphene:
Graphene tng hp c c tnh cht rt c bit. Chuyn ng ca cc electron
rt nhanh, electron dng nh khng c khi lng v chuyn ng gn bng vn tc
nh sng. Electron trong graphene c vn tc ln gp 100 ln electron trong silicon.
Chuyn ng ca electron khng tun theo phng trnh Schro dinger m tun theo
phng trnh Dirac cho cc ht khng c khi lng. Ht ny mang y cc tnh
cht ca ht Dirac. Ht Dirac c mnh danh l cc ht ma v nhng biu hin k d
ca n. l trong trng hp no s dch chuyn ngc chiu tc dng ca in
trng, ngc chiu tc dng ca lc.
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 41

i vi graphene, cc nguyn t dao ng ti nhit phng to ra mt in tr
sut vo khong 1.0 microOhm.cm. in tr sut ca graphene nh hn in tr sut
ca ng n 35% v l in tr sut thp nht c bit n ti nhit phng. iu
ny c gii thch nh sau: trong cc mu graphene c ch to khng c sch
lm tng in tr sut ca graphene. Do , in tr sut trung bnh ca graphene
khng nh bng in tr sut ca ng ti nhit phng. Tuy nhin, graphene li c
rt t electron so vi ng, do trong graphene dng in c vn chuyn bi mt
s t electron c vn tc nhanh hn nhiu ln so vi cc electron ca ng.
i vi cc vt liu bn dn, tiu chun v tnh linh ng c s dng xc
nh cc electron chuyn ng nhanh mc no. Gii hn tnh linh ng ca electron
trong graphene c xc nh nh dao ng nhit ca nguyn t v gi tr ny vo
khong 200.000 cm
2
/Vs ti nhit phng. Trong khi silicon l 1.400 cm
2
/Vs,
indium antimonide l 77.000 cm
2
/Vs. Electron ca graphene c linh ng cao nht
so vi cc cht bn dn thng thng.
Cc nh khoa hc chng minh rng mc d gii hn tnh linh ng ca
graphene nhit phng cao mc 200.000 cm
2
/Vs, cc mu vt hin nay c tnh
linh ng nh hn vo khong 10.000 cm
2
/Vs v cn phi n lc ci tin rt nhiu.
Do graphene c cu to ch vi mt lp nguyn t, cc mu vt hin nay phi c t
trong cht nn l silicon ioxit. in tch b gi trong cht nn silicon ioxit c th nh
hng n cc electron trong graphene lm gim tnh linh ng. Dao ng ca cc
nguyn t silicon ioxit bn thn chng cng c th c nh hng n graphene
thm ch cn ln hn nh hng t dao ng nguyn t ca chnh n. Nhng v cc
phonon trong bn thn graphene li khng h c tc dng trong vic phn tn electron,
do hiu qu ny tr nn rt quan trng trong graphene.
Graphene c tnh dn in v dn nhit tt
dng tinh khit, graphene dn in nhanh hn bt c cht no khc nhit
bnh thng. Graphene c th truyn ti in nng tt hn ng gp mt triu ln. Hn
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 42

na, cc electron i qua graphene hu nh khng gp in tr nn t sinh nhit. Bn
thn graphene cng l cht dn nhit, cho php nhit i qua v pht tn rt nhanh.
bn v cng ca graphene:
bn:
Graphene bn hn thp 200 ln.Nhng tnh ton v th nghim kim chng
bn ca graphene kt qu cho thy c sc bn ni ti ca n. Graphene c th
xem l mt gii hn trn cho sc bn ca vt liu- ging nh kim cng l cht cng
nht.
cng
Graphene c cu trc bn vng ngay c nhit bnh thng. cng ca
graphene lch khi biu so vi cc h cht liu khc. y l nh cc lin kt
carbon- carbon trong graphene cng nh s vng mt ca bt c khim khuyt no
trong phn cng cao nht ca mng graphene.
3.3. Phng php tnh
Mc ch nguyn cu
Nhng c tnh vt tri ca graphene nh bn hn thp, dn in tt hn bt
k vt liu no c khm ph trc . Kt cu mng graphene c nh hng ln
n t tnh vt tri ca n. Trong , hot ng ca electron trong mng graphene
chnh l im m cc nh nghin cu quan tm nhiu nht. Vi truyn dn tt, cc
nh khoa hc ang k vng s ch to ra mt loi linh kin in t, transistor, quantum
dot bng graphene thay th cho linh kin bn dn hin nay s dng vt liu silic l ch
yu. Trong ti ny, chng ti tin hnh kho st mng graphene c cu trc hu hn.
Vi mng li carbon u n ch vi kch thc hai chiu: di v rng, s sp xp
hon ho nh vy gip n kh lng b v vi nhng yu t tc dng thng thng. Khi
mng graphene cng ln mc hon ho trong cu trc cng cao.


Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 43

Cc bc nghin cu :
Tnh cu hnh bn ca mu graphene C
24
H
12
bng 2 phng php
B3LYP v PBEPBE. Phn tch cc mode dao ng trong h, xy
dng ph IR.
S dng cu hnh c ti u bng phng php B3LYP kho
st s co gin khong cch C-C trong ba trng hp khc nhau,
sau so snh vi trng hp graphene pha tp.
Phng php nguyn cu
Qu trnh kho st c thc hin bng phng php tnh ton s dng chng
trnh tnh Gaussian 03W, ng thi cng kt hp vi cc phn mm GausView 5.0,
Origin 8.0. Thng s hnh hc ca cu trc c ti u ha v tnh tn s dao ng
bng l thuyt phim hm mt vi cc phim hm c s dng l B3LYP v
PBEPBE kt hp vi b hm c s khuch tn 6-31G. K n s dng cu hnh ti
u tin hnh kho st s co gin khong cch carbon nhng v tr khc nhau, phng
php tnh c s dng l B3LYP vi b c s 6-31G.
3.4. Kt qu v tho lun
Tnh ton cu hnh bn
Phng php tnh c s dng u tin l B3LYP thi gian tiu tn cho qu
trnh ny l 5 gi 30 pht. Trong hai trng hp nng lng u c quy v n v
tnh l kcal/mol(1 hartree= 627.509 kcal/mol)

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 44

Hnh 3.4: Mu graphene C
24
H
12
c ti u bng phng php B3LYP

Khi s dng phng php PBEPBE, thi gian tiu hao cho vic tnh ton cu
hnh bn ca h gn gp i so vi phng php u tin ( trong 11 gi). Cc gi tr
thu c sau khi ti u cu hnh so vi thc nghim sai lch khng ng k. Trong ,
mu graphene C
24
H
12
c kho st c gi tr ti u v gc v di lin kt (xem
bng 3.1 v bng 3.2) c tnh bng phng php B3LYP cho cu hnh tt v gn vi
thc nghim nht. Khong cch gia cc nguyn t c tnh bng v gc lin kt
c tnh theo . D s dng phim hm B3LYP hay PBEPBE th nng lng cn
cung cp gy ra nhng thay i trong phin graphene (c v gc v di lin kt)
u rt ln.
Trong bng 3.1 v bng 3.2, lch c tnh so vi gi tr c chn ti v tr
C trong cng v gn st vi gi tr thc nghim nht (1.42 ). Nhng nguyn t C
xung quanh v tr C c kho st c sai lch kh thp. i vi mu C
24
H
12
ti u
bng B3LYP , v tr xem xt [5,4] c di lin kt 1.427 v gc lin kt 119.9
o
ti
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 45

v tr [6,5,4]; nhng C xung quanh c di bng 1.421, 1.427, 1.427, 1.421 ln
lt ti v tr [5,11], [3,4], [6,5], [4,10] v cc gc 118.76
o
, 119.9
o
, 119.9
o
, 118.78
o
ln
lt ti v tr [23,12,6], [12,6,5], [5,4,10], [4,10,18] ...(xem bng 3.1). Gc lin kt
cng c xt tng t (xem bng 3.2). Nh vy, cng i su vo bn trong tnh n
nh cng cao. Vi nhng tm graphene thc t c kch thc rt ln s n nh ca n
cng c th hin r hn. Bn cnh , chng ti phn no kim chng c
ng tin cy ca phng php c s dng.
B3LYP
(C
24
H
12
)
lch
%
PBEPBE
(C
24
H
12
)
lch
%
1.427[5,4] 0 1.434[5,4] 0
1.421[4,10] -0.6 1.434[4,10] 0
1.424[10,18]
-0.3
1,431[10,18]
-0.3
1,427[5,6]
0
1.434[4,8]
0
1.422[6,12] -0.5 1,433[4,5] -0.1
1.424[12,23]
-0.3
1.431[5,6]
-0.3
1.423[12,22]
-0.4
1431[5,16]
-0.3
1.421[5,11] -0.6 1.434[8,14] 0
1.424[10,19] -0.3 1.431[11,12] -0.3
1.427[1,6] 0 1.434[3,4] 0
1.427[3,4] 0 1.434[9,10] 0
1.424[7,24] -0.3 1.430[1,2] -0.4
1.422[7,1] -0.5 1.434[2,3] 0
1.427[1,2] 0 1.434[3,7] 0
1.427[2,3] 0 1.434[7,10] 0
1.422[3,9] -0.5 1.433[10,30] -0.1
1.424[9,17] -0.3 1.431[30,35] -0.3
1.424[17,13] -0.3 1.431[2,23] -0.3
1.421[2,8] -0.6 1.434[7,25] 0
1.423[9,16] -0.4 1.431[30,29] -0.3

Bng 3.1 : Khong cch C-C ca mu graphene C
24
H
12
c ti u bng
phng php B3LYP v PBEPBE . H s trong [] l v tr C c xt

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 46

B3LYP
(C
24
H
12
)
lch
()
PBE
(C
24
H
12
)
lch
()
118.76[23,12,6] -1.23 119.99[6,5,4] 0
119.99[12,6,5] 0 121.22[13,14,8] 1.23
119.99[6,5,4] 0 122.45[14,8,15] 2.46
119.99[5,4,10] 0 121.22[8,15,16] 1.23
118.76[4,10,18] -1.23 118.77[24,7,1] -1.22
121.23[22,21,11] 1.24 119.99[7,1,2] 0
122.46[21,11,20] 2.47 119.99[1,2,3] 0
121.23[11,20,19] -1.23 120.00[2,3,9] 0.1
118.76[24,7,1] 1.24 118.77[3,9,17] -1.22
119.99[7,1,2] 0 118.77[23,12,6] -1.22
119.99[1,2,3] 0 120.00[12,6,5] 0.1
119.99[2,3,9] 0 119.9[5,4,10] -0.9
118.76[3,9,17] -1.23 118.77[4,10,18] -1.22
121.23[13,14,8] 1.24 121.22[22,21,11] 1.23
122.46[14,8,15] 2.47 122.46[21,11,20] 2.47
121.23[8,15,16] 1.24 121.22[11,20,19] 1.23

Bng 3.2: Gc lin kt gia C vi 2 nguyn t k cn ca mu graphene C
24
H
12
kho
st bng phng php B3LYP v PBEPBE.

H s trong du [] l v tr C c xt.












Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 47

Phn tch ph dao ng ca C
24
H
12



Hnh 3.5: Ph dao ng ca graphene kho st bng phng php
PBEPBE v B3LYP
Nhn xt
Lin kt C-H trong mng xut hin ba loi dao ng : 2 rock, bend v stretch c
s sng ln lt l 570.136 cm
-1
, 785.534 cm
-1
, 1346.42 cm
-1
, 3197.82 cm
-1
. Trong
C-H stretch 3197.82 cm
-1
hp thu hng ngoi cng cao 581.231. Lin kt C=C
stretch dao ng s sng 1669.24 cm
-1
c cng IR tng i thp 50.77. Hai dao
ng C-C stretch 879.735 cm
-1
v 1167.12 cm
-1
c cng IR ln lt l 374.123
v 41.45
Dao ng l i xng hay bt i xng th dao ng ca ton h khng xut
hin dao ng ring l. Do , khi h chu tc dng ca nhn t bn ngoi (chng hn
Wave No. (cm
-1
)
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 48

nh p sut, tc dng lc) cng s khng d ph v mch. V khi chu tc dng bn
ngoi th dao ng h tr thnh dao ng chung ca ton mng.
Kho st qu trnh co gin lin kt gia carbon v carbon ti cc v
tr khc nhau
Mu c em kho st l mu ti u ha bng phng php B3LYP/6-31G.
Qu trnh c thc hin trong ba trng hp. Tin hnh scan tng trng hp bt u
trong khong gi tr t 1.4 n 2.5. Khong cch co gin c c nh l 0.1
trong tt c ba trng hp. Nng lng c tnh theo n v l kcal/mol.
Trng hp 1: Co gin khong cch carbon pha ngoi ti v tr 24-25

Hnh 3.6: Carbon trong mu kho st ti v tr 24 v 25
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 49


Hnh 3.7: S thay i khong cch gia 2 nguyn t carbon ti v tr 24 v 25
Trng hp 2: Co gin khong cch carbon pha trong v ngoi vng ti v
tr 7-25

Hnh 3.8: Carbon trong mu kho st ti v tr 7 v 25
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 50


Hnh 3.9: S thay i khong cch gia 2 nguyn t carbon ti v tr 7 v 25
Trng hp 3: Co gin khong cch carbon bn trong vng ti v tr 7-10

Hnh 3.10: Carbon trong mu kho st ti v tr 7 v 10

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 51


Hnh 3.11: S thay i khong cch gia 2 nguyn t carbon ti v tr 7 v 10

Scan
Coordinate
Mu
kho st
Delta E
(kcal/mol)
1.5 C7-10 3.74
C7-25 2.56
C25-24 3.49
1.6 C7-10 12.98
C7-25 10.78
C25-24 11.82
1.7 C7-10 25.44
C7-25 22.10
C25-24 22.70
1.8 C7-10 39.76
C7-25 34.98
C25-24 34.74
1.9 C7-10 55.12
C7-25 48.52
C25-24 47.09
2.0 C7-10 82.69
C7-25 62.23
Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 52

C25-24 68.21
2.1 C7-10 99.31
C7-25 73.29
C25-24 68.21
2.2 C7-10 116.15
C7-25 89.24
C25-24 79.69
2.3 C7-10 133.18
C7-25 102.27
C25-24 90.62
2.4 C7-10 150.39
C7-25 114.91
C25-24 110.76
2.5 C7-10 167.81
C7-25 127.166
C25-24 120.00

Bng 3.3: Gi tr nng lng thu c khi co gin khong cch ti v tr carbon khc
nhau
Nhn xt
Trong c ba trng hp, khi khong cch co gin cng ln nng lng c xu
hng tng ln, trong ti v tr C7 v C10 nng lng l cao nht. Nh th trng
hp 3 l kh gin nht.

So snh nng lng co gin ca graphene tinh khit v pha tp
Khi so snh vi trng hp graphene c pha tp nito[5], nng lng co gin
tng ng lun thp hn khi graphene trong trng thi tinh khit (hnh 3.19).

Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 53


Hnh 3.12: Graphene pha tp N ti
v tr C9-N36[5]

Hnh 3.13: Graphene pha tp N ti v tr
C4-N36[5]

Hnh 3.14: Graphene pha tp N ti v tr
C5-N35[5]


Kha lun tt nghip i hc 2011 GVHD: TS. L Minh Hng

SVTH: Trn Nguyn Trang 54


Hnh 3.15: Nng lng co gin trong trng hp graphene tinh khit v pha tp
nito. ng t nt biu din nng lng co gin khi c pha tap.[5]

Nhn xt
So snh s gin lin kt gia graphene tinh khit v pha tp tng ng trong
tng trng hp (hnh 3.15) ta thy: khong cch 2.1 ti v tr C7-C10 c nng
lng gin lin kt cao hn C9-N36 l 42.03 kcal/mol, v tr C7-C25 so vi C4-N36 l
11.08 kcal/mol, cn v tr C24-C25 so vi C5-N35 l 9.88 kcal/mol. Trng hp gin
ti C7-C10 v C9-N36 c nng lng ln nht. gim nng lng tng ng trong
tng trng hp nh vy cho thy, d co gin ti v tr lin kt no th graphene tinh
khit lun c nng lng cao hn. Nh vy trng hp graphene tinh khit kh gin
nn s bn hn graphene pha tp.
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CHNG 4 KHO ST VT LIU (ZnO)
2

4.1. Cu hnh v trng thi h nhiu electron
Cu hnh electron l s phn b cc electron trong h lng lng t. vic xc
nh cu hnh electron c ngha quan trng v n lin quan ti vic xc nh phng
php tnh thch hp.
Tuy nhin cu hnh electron cha m t y trng thi cc electron nn t
cng mt cu hnh c th c nhiu trng thi khc nhau. N cn ph thuc vo trng
thi spin ca h, xc nh c thng qua bi. bi ca trng thi bng 2S+1 cho
bit s electron c thn trong trng thi .

S electron
c thn
S 2S+1 Trng thi h
0 0 1 Singlet
1 1/2 2 Doublet
2 1 3 Triplet
3 3/2 4 Quartet
4 2 5 Pentet

C th phn loi cu hnh electron nh sau:
Cu hnh v ng: l cu hnh trng thi c bn, c n orbital b chim bi 2n
electron. Cu hnh ny tng ng vi trng hp suy bin nng lng v 2 eletron c
spin i song song cng 1 orbital b chim c cng nng lng. H khng c electron
c thn nn trng thi singlet.
Cu hnh v m: l cu hnh trng thi c bn m h c 2n+1 electron th c n
orbital b chim ch bi 2n electron v orbital th n+1 b chim ch bi 1 electron. Do
cn 1 electron c thn nn h trng thi doublet.
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Cu hnh hn ch l cu hnh c n electron th 2m (m<n) electron ghp i,
cn n-2m electron chim n-2m orbital khc nhau. Cu hnh ny ng vi trng thi v
m hoc trng thi kch thch.
Cu hnh khng hn ch: l cu hnh ng vi trng hp hai hm spin o, [ c
cc hm khng gian khc nhau. Trong trng hp h trng thi c bn, s electron
ca hm spin o ln hn ca hm spin [. y l trng hp khng suy bin nng
lng. Cu hnh ny c th s dng cho h ng, m v h trng thi kch thch.
4.2. Hng nguyn cu
Trong trng hp (ZnO)
2
cluster, chng ti s xem xt nng lng nhiu trng
thi spin i vi nhng cu hnh hnh hc khc nhau ca cluster ny.
Cc tnh cht ca ZnO cng c tng cng khi n dng nano. Nhiu nghin
cu v ZnO cluster c tin hnh. Trong mt bi bo gn y, nhm tc gi Xueli
Cheng, Feng Li, Yanyun Zhao ti trng i hc Taishan, Trung Quc tin hnh kho
st tnh n nh ca (ZnO)
n
(n= 1-12) cu trc nano bng phng php DFT thay v
phng php gi th c nghin cu trc , phng php tnh c s dng l
B3LYP vi b c s 6-31G [3]. Kt qu cho thy: khi n= 1-5 cu trc vng n nh,
n > 10 th cu trc vng khng tn ti. cu trc 3D, n 5 n nh hn cu trc vng.
Bi bo cn cho rng vi cu trc 3D khi n cng ln th s c li hn v mt nng
lng.
Da vo d liu c c t [3], chng ti tin hnh kho st s n nh ca
(ZnO)
n
(n=1,2) vi cu hnh khc nhau bng hai phng php B3LYP v PBW91 vi
nhng b c s cao hn l 6-311G, 6-311G*, 6-311G (d,p), CC-PVDZ. Ton b qu
trnh tnh s dng phn mm Gaussian 03W.
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Hnh 4.16: Cu hnh (ZnO)
n
c kho st
Khi tin hnh optimize (ZnO)
n
nhng b c s cao hn, kt qu cho thy cu
hnh (2b) v (2c) khng tn ti. Da vo y chng ti tip tc s dng nghin cu
cc bc tip theo trong lun vn.
4.3. Phng php tnh ton
Qu trnh kho st c thc hin bng phng php tnh ton vi phn mm l
chng trnh tnh Guassian 03W, c kt hp vi cc phn mm Gaussview 5.0. Tham
s hnh hc ca cu trc trc ht c ti u ha bng l thuyt phim hm mt
vi hm lai ha thng dng B3LYP cng b hm c s phn cc 6-311G(d,p). Phng
php B3LYP l mt trong nhng phng php cho kt qu nng lng tng i chnh
xc, phng php ny s c dng trong ton b qu trnh kho st.
Cc bc nghin cu
Kho st trng thi bn ca spin nhiu cu hnh (ZnO)
2
khc nhau trong
chn khng trong trng hp ZnO t xa nhau.
Thay i cu hnh khi ZnO t gn nhau trong khong gi tr cho trc,
kho st trng thi bn trong cc trng hp spin.






(1) (2a)
(2b)
(2c)
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4.4. Kt qu v tho lun
Kho st trng thi bn ca spin nhiu cu hnh (ZnO)
2
khc nhau

Hnh 4.17: Biu nng lng hnh thnh (ZnO)
2
trong ba trng thi spin
khc nhau

Nhn xt
Trong trng hp hai nguyn t ZnO t xa nhau, biu nng lng cho thy,
nng lng trng thi singlet cao hn so vi triplet v pentet. Nh vy, trng thi
spin triplet v pentet th cu hnh (ZnO)
2
bn hn.
Gii thch
trng thi c bn, mi nguyn t Zn v O c mt electron c thn. Khi hnh
thnh lin kt, phn t ZnO khng tn ti electron c thn no.
STT mu
N

n
g

l

n
g

(
k
c
a
l
/
m
o
l
)

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Hnh 4.18 : Cu hnh (ZnO)
2
trng thi singlet
Ti trng thi c bn (ZnO)
2
c hnh thnh khng tn ti electron c thn,
y l trng thi singlet. Nng lng trng thi ny cao, nn (ZnO)
2
trong trng hp
ny l km bn nht hoc c th l khng tn ti. (hnh 4.21)

Hnh 4.19: Cu hnh (ZnO)
2
trng thi triplet
Khi hai phn t ZnO dao ng v xy ra tng tc, ZnO s tng tc vi phn
t cn li. Nhng electron c thn trong mi phn t ZnO s d dng ghp cp vi
nhau. V c hai electron ghp cp nn h (ZnO)
2
c hnh thnh cn 2 electron c
thn, theo l thuyt v cc trng thi spin y l trng thi triplet. Trng thi ny bn so
vi singlet v nng lng cn cung cp hnh thnh lin kt s thp (hnh 4.22).


Hnh 4.20: Cu hnh Zn
2
O
2
trng thi pentet
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Ngc li, khi phn t ZnO dao ng v khng tng tc vi phn t cn li,
nn mi ZnO vn c 2 electron c thn. Khi phn t (ZnO)
2
hnh thnh trong h tn
ti 4 electron c thn (hnh 4.23) y l trng hp h trng thi pentet. Trong
trng hp ny h cng trng thi bn.
Kho st nng lng h phn t (ZnO)
2
ng vi s thay i cu hnh
cc trng thi spin khc nhau
S dng phn mm Matlab vit chng trnh to 1000 input cho mi trng
hp. Chy chng trnh Gaussian thu c kt qu nng lng tng ng. Phim hm
B3LYP vi b c s phn cc 6-311g (d,p) c s dng trong sut qu trnh kho st.
Trc khi thc thc hin tnh ton, phn t (ZnO)
2
c ti u ha cu hnh
trng thi bn. Cc thng s ti u ha c th nh sau : r
1
=1.8998734;
r
2
=1.90024288;
1
=76.90399513; r
3
=1.90036713;
2
=103.06304269; =-0.00000002.
Qu trnh tnh ton c thc hin bng cch dch chuyn v tr cc nguyn t trong
phn t vi khong random c nh trc vi gi tr c th nh sau:


r
1
1.79987342.0998734
r
2
1.800242882.10024288
r
3
1.800367132.10036713

1
66.9039951386.90399513

2
93.06304269113.0630427

-9.9999999810.00000002

Hnh 4.21: Mu phn t (ZnO)
2
c
ti u bng Gaussian

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Hnh 4.22: Nng lng ca h (ZnO)
2
tng ng vi s thay i cu hnh trong
ba trng thi spin

Nhn xt
Biu hnh 4.22 cho thy nng lng ca (ZnO)
2
trng thi singlet l thp
nht. Nh vy, khi trng thi singlet h c cu hnh bn.
Gii thch
Trng hp ny, hai phn t ZnO t gn nhau, cc thng s c th hin
trong hnh 4.21. Khi t gn nhau, cc electron trong phn t s bt cp vi nhau, h
(ZnO)
2
hnh thnh khng cn tn ti electron c thn no (trng thi singlet). Cu
hnh trng thi c bn ny n nh bi s lp y cc orbital ca cc electron. Do
, trng thi singlet c nng lng thp nh kt qu tnh ton thu c. electron
STT mu
N

n
g

l

n
g

(
k
c
a
l
/
m
o
l
)

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c th thay i trng thi t singlet sang triplet, hay pentet th phi cn tiu tn mt
nng lng ln hn nhiu so vi nng lng ti trng thi singlet. Mc khc, s thay
i di lin kt v gc hp bi cc nguyn t dao ng trong mt khong gi tr rt
b. Chnh v gi tr khng ln ny m ta c th xem cc nguyn t trong h ch nh dao
ng xung quanh v tr cn bng. Nh vy, trng thi singlet l trng thi bn nht
trong trng hp ny.





















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KT LUN

Trong thi gian thc hin ti, ti c iu kin tip cn phng php nghin
cu bng m phng my tnh. ng thi c iu kin hc thm k nng s dng mt
s phn mm tnh ton phc v cho qu trnh nghin cu : Gaussian 03W, Gauss View
05
ti m phng c cu trc ca phin graphene hu hn bng phng
php phim hm mt DFT, da vo cu hnh thu c cho thy s n nh trong
cu trc ca graphene ngay c kch thc nh. Khi so snh vi gi tr c c t thc
nghim: di lin kt C-C lch khong 0-0.6 % , gc lin kt lch khong 0-2.47 %.
Qua cng cho thy ng tin cy ca phng php tnh c s dng.
Tip , khi gin mnh C-C ti v tr khc nhau, graphene s mt dn tnh
aromatic, nng lng kch hot cho vic ny l rt ln. Mc khc, khi so snh vi
graphene pha tp N, nng lng gin C-C ln hn C-N. Qua phn tch ph IR theo l
thuyt v kho st s bt n nh trong cu trc ca graphene nh vy gin tip
chng minh, d kch thc rt nh vt liu ny cng rt bn.
Bn cnh , ti cng kho st cc trng thi bn spin nhiu cu hnh
(ZnO)
2
khc nhau trong chn khng. Khi (ZnO)
2
t gn nhau trng thi singlet l bn
nht, khi (ZnO)
2
t xa nhau th trng thi triplet v pentet bn.
ti cng cho thy th mnh v s ng tin ca phng php tnh ton m
phng, nhng kt qu tnh ton l thuyt thu c c th lm nn cho cc qu trnh
thc nghim sau ny. Ngoi ra, phn mm Gaussian c s dng trong ti
chng t l mt cng c mnh v hu ch phc v cho vic nghin cu v tnh ton.




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TI LIU THAM KHO

Ting vit
[1] Nhp mn c hc lng t (1999) tc gi Hong Dng, NXB Gio Dc.
[2] C s vt l cht rn (2001) tc gi L Khc Bnh, Nguyn Nht Khanh, NXB
HQG TPHCM.
[3]Ha l cu to phn t v lin kt ha hc(2002) tc gi Nguyn Vn Xuyn, NXB
Khoa hc v K thut.
Ting anh
[1] Introduction to computational Chemistry (1999), Frank Jensen, Odense University,
Denmark.
[2]Exploring Chemistry with electronic Structure Methods(1996), James B.Foresman
and AEleen Frisch.
[3] Xueli Cheng, Feng Li, Yanyun Zhao,A DFT investigation on ZnO clusters and
nanostructures (2008), Elsevier B.V, Journal of Molecular Structure: THEOCHEM 894
(2009) 121127.
[4] S.Reich, J.Maultzsch, and C.Thomsen, Institute de Material de Barcelona(CSIC),
Tight-binding description of graphene, Physical Review B 66, 035412.
[5] Phm Tun t, , Seminar thc nghim: M phng phn t hu hn graphene vi
s pha tp ca N, v s t kt ni ca C-N trong h ny. Kho st trng thi bn ca
cc spin nhiu cu hnh (ZnO)
2
khc nhau trong chn khng (2011), BM. Vt liu v
linh kin mng mng, Khoa Khoa hc vt liu, Trng H Khoa hc t nhin.

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