LUC  Nguyn Th Nguy I HC QUI
TRƢỜNG ĐẠI HỌC KHOA HỌC TỰ NHIÊN

Nguyễn Thị Nguyệt Ánh
NGHIÊN CỨU MỘT SỐ PHÂN TỬ CÓ CHUYỂN PHA SPIN LUC i  N 2012

i   LUC  Nguyn Th Nguy LỜI CẢM ƠN

L c nhn th
Nguyn Anh Tun, cng dn, bt
lu.
i li c
b  Thp, Khoa Vi
hc Khoa hc T t nhiu kin thc b 
Cui li c
  t thi gian qua.

 12 12 
Hc 
Nguyễn Thị Nguyệt Ánh

-Kohn th nht 13
2.1.4. 









-Sham 16
 18
Chƣơng 3. Cấu trúc hình học, cấu trúc điện tử và đặc trƣng chuyển pha spin
của phân tử Mn(pyrol)
3
(tren) 19
3.1. Trp 19
3.1.1. Cc 19
3.1.2. Cn t 21
3.2. Tr 23
3.2.1. Cc 23
3.2.2. Cn t 24
3.3. Mt s a chuyn pha spin 26
3.3.1. S i c c 27
3.3.2. S chuy 28
3.3.3. S bing 31
Chƣơng 4. Cấu trúc hình học, cấu trúc điện tử và đặc trƣng chuyển pha spin
của phức chất [Fe

LUC  Nguyn Th Nguy DANH MỤC HÌNH VẼ

c c Mn(pyrol)
3

ng. 1
 P c Mn
III
. 2
 chuyn tr ng ca
nhing cng c 4
ng dt b hin th c chuyn pha spin. 4
: Cc c Mn(pyrol)
3
 ng 

c biu din b ti b m
3
. 23
3.6: Cn MnN
6
c Mn(pyrol)
3
(tren)  tr 23
 3.7:   

  c  n t 





    
Mn(pyrol)
3
(tren)

 tr HS. 25
t s qu  gn mc Fermi c Mn(pyrol)
3
(tren)
trong tr ti b m
3
. 26
3.9: S   Mn(pyrol)
3












 3d c Fe
III
, (b) Trng 
LS, (c) Tr  spin trong tr  spin
trong tr ti b m
3
. 37
: Bc tranh m bin dn t ca phc cht [Fe
III
(salten)(mepepy)]
 n t so vi tr (


c biu din bn t
so vi tr (

c biu din b 
t). M ti b m
3

(4-NO
2
-py)
2
]
trn 42
  C   n Co-N
2
O
4
c

[Co(dioxolene)
2
(4-NO
2
-py)
2
]
tr 43
5.4: (a) 









LUC  Nguyn Th Nguy DANH MỤC BẢNG BIỂU

B t MnN c Mn(pyrol)
3
(tren)  trng t
c t thc nghit. 20
B t Mn-N c Mn(pyrol)
3
(tren)  tr
c t thc nghit. 24
Bng 3.3 t Mnt NMnN (
o
)  trng
a  [Mn(pyrol)
3
c t kt qu c
nghi d  . 27
B N1N6 trong tr
LS

tr
HS
) c Mn(pyrol)
3
(tren). 31


LUC  Nguyn Th Nguy Các ký hiệu & từ viết tắt

AO: Qu  (Atomic orbital)
t phi (Density functional theory)
E: Tng
E
xc
i
HOMOn: Qu  th n i mc HOMO
HOMO: Qu  cao nht b chim (Highest occupied molecular orbital)
HS: Spin cao (High spin)
K
LS: Spin thp (Low spin)
LUMO: Qu  thp nh chim (Lowest unoccupied molecular
orbital)
LUMO+n: Qu  th n c LUMO
m: M
MO: Qu  (Molecular orbital)
n: i
Png kt cn t
S: Tng spin
SCO: Chuyn pha spin (Spin-crossover)
TS: Trn (Transition state)
U: Th n Coulomb

ng e

 d
7


  kim
loi chuyn tip Mn
III
, vi cn t d
4
 ng hp
cht ca Mn  tr  c bao quanh bi 6
 ng phi t kin MnN
6
 bao
 , v Mn(pyrol)
3


LUC  Nguyn Th Nguy phi t MnN
6
 c bao xung quanh b c
ch .1.
 o 3d c Mn b c
mc e
g
t
2g

g
tr t li v mng so vi vic
n t  bn t 3d ca ion Mn
III
nm  t
2g
, trong
n t p v S = 1, g
trp (Low spin, LS).
e
g
tr i v mng so vi vic
n t  n t 3d ca ion Mn
III
nm  trt
2g
n
t th  nm  tre
g
ng h bn t 3d ca ion
Mn
III
 
spin, HS).
 t gi nh   tn
ti  c hai tru kin nhi
c minh h 1.2.
 c t, vic          SCO

II

III
va ion Co
III

ng gi nh  tr, hing SCO
hiy  nh Mn
II
vi cn t d
5
, hp cht
ng nh  trc li, v cha ion Fe
III

n t 3d y.
 


 

[3,24]


cao [15].


1.3(a)  
s ph thuc ca tr c SCO.  nhi thp,
 tn ti  trp LS,  nhi  tn ti  tr
spin cao HS.    chuyn tra nhi 
 nhi n nhi T

c bit nng nhi t T
1
n T
2
,
s d  chuyn t
trp sang trc lc minh h
1.3(c). V  c s d
nh  c thc hin bi nhi hoc


1.3: 

n pha spin, tng spin c thay 
t b chuyn m.
  
c ng dt b hin th. LUC  Nguyn Th Nguy 1.4
 





 (DFT).

LUC  Nguyn Th Nguy C 2
PHƢƠNG PHÁP NGHIÊN CỨU

2.1. Giới thiệu về lý thuyết phiếm hàm mật độ (DFT)
ng t u h n t i gii
  ca h a 3N bin s. Cho
n hi i gii vng h 
n ti v   gii g
 mt gin ti
a h nhin t.
t phi (Density-
tip c hin thi nhiu ht
t hii dn tng cng t 
 t ca h n t , vt rm ct yu
t ca h in t c biu di
m n t ca h a 3 bin t a
3N bin t ng tm l
hic s dng nhiu nht) trong vit c















c gi










:
)1.1.2(), ,(), ,(
2
1
)(


























-Openheimer [1]. 








nhau s 







a h 







:
)2.1.2(), ,(
1 M
RREE



 -(E
nn
c t
ng:











  c l gi nhiu ht.
  t DFT, 









 c biu di t
phia m n t (E[(r)]) 





 p c
chuy nhiu hn t y cho








phi
























phi











 E[(r)]. 










E[(r)].
2.1.2. : Thomas-










.  : 







 ng
nhi v











 i h s 2

















 







 . 
 dn dt m

 


Thomas-Fermi.




:
)5.1.2(
)(
)(
2
)(
)()(
2
)(
)()()(
2
)(
)(
2
)(
2
2
*
2
2
2
*
2
*2
2
*
2
2
2

m
r
rdr
r
e
Z
m
rE








































 r). 
 r). 





















 N, 






0 K, 

 thi









, 


n
x
, n
y
, n
z
= 1, 2, 3, R 

, 
















 






















h
mlR

LUC  Nguyn Th Nguy 










g() 






















 (





e
f

0 







:
)10.1.2(
,0
,1
)( 














F








.


















2
5
8
2
4
)()(2
2/53
2/3
2
0
2/33
2/3
2
F
l
h
m
dl
h
m
dgfE
F












 n t,








  


F







N 



V, 

:

thay 
F


(2.1.12) (2.1.11), :
)13.1.2(
8
3
10
3
3/5
3
3
3/2
2














l







. 










, :
)14.1.2(871.2)3(
10
3
,)(
)()3(
10
3
)(
8
3
10
3














FF
TF
C
m
rdrC
m
rdr
rdr
m
h
T







 ,  -














, 





. 























N 



, :
)17.1.2(
)()(
2
1)(
)()]([
21
21
21
3/5
rdrd
rr

)18.1.2(, ,, ,), ,,, ,( )(
111
2
111 NiiNiii
rdrdrdrdrrrrNr


 





 (2.1.17), 







 . 

























 . , 




 c t  ng nht, 














 -Fermi-Dirac
(TFD) [6,28], Thomas-Fermi-Weizsacker (TFW) [28,38],  -
Fermi-Dirac-Weizsacker (TFDW hay TFD-[2,21,22,28,39,40].
























, :
)19.1.2(][][][

xTFTFD
EEE 



:
 
)20.1.2(7386.0,)(][][
3/1
3
4
3
3/4




xxDx
CrdrCKE



















 [38], 




















 rd
r
r
T
W

















:
)22.1.2(][][][


WTFWTF
TTT 







[16].




















T[] 

c



 n, 

 -







 t s g
i v







 ,  . 



 m
 E[], 
.  .
2.1.3. 








N



















), ,,(
21 N
xxx



 -Openheimer , 









 (






LUC  Nguyn Th Nguy )24.1.2(
1
2
1
)(
2
1
ˆ
111
2







:
)5.1.2()(
1





M
i
i
Rr
Z
rv





















) 








 :
)26.1.2(, ,,, ,), ,,, ,( )(
111
2
111 NiiiNiii
xdxddsxdxdxxxxNr


 





























)(r


. , 




)(r



)27.1.2()(

 rdrN



,
)(r



[] 
-



V
ee
[]. 
)(r









, 








, 










)(r



[18].


-V
ne
,












-



 V
ee
,  T 



 
)(r



1
)(
)( )(
)( )(
)(
)(
111
11
2
21
2
11
1
2
1
2
1
1
1
2
1
1
*



    
  

 









rrvrd
rrvrd
N
rrvrd
N
r
N
rvrdr
N
rvrd
dsxdxdrvrdxdxddsrvrd
xdxdrvxdxdrv
xdxdrv
xdxdrvV
timesN
NNN
NNNNN
NNN
N
i
Ni
N



:
)29.1.2()()(][

 rdrrvV
ne



Ti u di











-



 V
ee




1
2
1

21
21
21
321
2
21
21
321
2
21
21
1
2
21
)1(
1
2
1
1
2
21
1
1
2
1
































rr
NN
xdxd
rr
xdxd
rr
xdxd
rr
xdxd
rr
V
N
N
N
timesNN
N
NN
N
N
ji
N
ji
N
N
ji
ji
ee




321
2
21 N
xdxddsds
NN
rr

 





y, :
)32.1.2(][
)()(),()()(
),(
][
21
21
2121
21
21
21
21
21
21
termalnonclassicJ
rdrd
rr









J[]  . 










 ; 
 






.
T, Thomas-



 T[]. 


 

,  












  nhc tip
t qua s g m thp c
m b , 




















-Sham








  

















:
)33.1.2()(
2
1
ˆ
11
2










N
i
is
N
i
i