Gaussian 03 7

2
X

[1]
1

Hartree-Fock

Koopmans [2]

Vol.,No.2007.11

367

Kohn-Sham Kohn-Sham KohnSham Koopmans

[3]
Kohn-Sham Kohn-Sham
1990 Kohn-Sham

[4]Kohn-Sham [3]

[5,6]
[7] [8]

Gaussian 03

#
POP FULL
POPFULL 1 RHF/

STO-3G 1 1 5
5 1

Gaussian
Standard orientation
NOSYMM
Standard orientation

Molecular Orbital Coefcients

12...
iA1B2 O
V occupied orbital virtual orbital

EIGENVALUES a.u.1 a.u. 627.50955 kcal/mol

27.2116 eV1 5 5 6 7

368

Vol.,No.2007.11

Standard orientation:
--------------------------------------------------------------------Center
Atomic
Atomic
Coordinates (Angstroms)
Number
Number
Type
X
Y
Z
--------------------------------------------------------------------1
8
0
0.000000
0.000000
0.127141
2
1
0
0.000000
0.757972
-0.508564
3
1
0
0.000000
-0.757972
-0.508564
--------------------------------------------------------------------Rotational constants (GHZ):
698.6120361
436.4113211
268.6131520

**********************************************************************
Population analysis using the SCF density.
**********************************************************************
Orbital symmetries:
Occupied (A1) (A1) (B2) (A1) (B1)

Virtual
(A1) (B2)
The electronic state is 1-A1.
Alpha occ. eigenvalues -- -20.25156 -1.25762 -0.59393 -0.45975 -0.39262
Alpha virt. eigenvalues -0.58193
0.69284
Molecular Orbital Coefficients
i
1
2
3
4
5
(A1)--O
(A1)--O
(B2)--O
(A1)--O
(B1)--O
EIGENVALUES --20.25156 -1.25762 -0.59393 -0.45975 -0.39262 (occupied)
1 1
O 1S
0.99422 -0.23376
0.00000 -0.10405
0.00000
2
2S
0.02585
0.84439
0.00000
0.53822
0.00000
3
2PX
0.00000
0.00000
0.00000
0.00000
1.00000
4
2PY
0.00000
0.00000
0.61270
0.00000
0.00000
5
2PZ
-0.00417 -0.12289
0.00000
0.75591
0.00000
6 2
H 1S
-0.00559
0.15561
0.44921 -0.29505
0.00000
7 3
H 1S
-0.00559
0.15561 -0.44921 -0.29505
0.00000
6
7

M
(A1)--V
(B2)--V
(HOMO)
EIGENVALUES -0.58193
0.69284 (virtual)
1 1
O 1S
-0.12584
0.00000
2
2S
0.82038
0.00000
3
2PX
0.00000
0.00000
4
2PY
0.00000
0.95988
5
2PZ
-0.76356
0.00000
6 2
H 1S
-0.76926 -0.81477
7 3
H 1S
-0.76926
0.81477

M

(LUMO)

1 RHF/STO-3G
7 5
Highest Occupied Molecular Orbital, HOMO6
Lowest Unoccupied Molecular

Orbital: LUMO
HOMO NHOMOnext HOMO
LUMO
NLUMOnext LUMO
HOMO1LUMO1

STO-3G 7
5 7 7
1 7
2 1 3 3
OHH
4

Vol.,No.2007.11

369

STO-3G spdf
1S 2PX 1s 2px
1s2s2px2py2pz 1 1s
7
i

RHF/STO-3G 3 3
0.0
1S:1,O
0.0
2S:1,O
0.0
2PX:1,O
0.61270
2PY:1,O

0.0
2PZ:1,O
0.44921
1S:2,H
0.44921
1S:3,H

2PY:1,O 1
O 2py
1S:2,H
1S:3,H

2 3 H 1s 3
2py 2 1s

Gaussian GaussView [9]

moview [10]

1
2

3
4

3 1

Standard orientation
y z O H 2 a

3
1 2PY 0.61270

370

Vol.,No.2007.11

1
3

(a)

(b)

(c)

=
(d)

(e)

(f)

2(a) (b) 3
(c) (b) (d) 4
(e) (f)
(d)
1/21/3

1/41/9
0.44921 0.44921 2 3
1S

s
p d
4

r
x ly mz nexp
r 2 spd... lmn0, 1, 2, 3,...4

expr2 x ly mz n
py yexp
r 2 y y

2b
y
s 2
3
2c
3 moview 3a 3a
2c 2c

Vol.,No.2007.11

371

 2p

(a)

(b)

3moview RHF/STO-3G 3 4
4 s p
0.53822 0.75591 2d
2e
2f
4
4 moview 3b 3b 2f

d
4
d 8

5 d 1
d 4 dxy

Kohn-Sham Hartree-Fock
d
d LUMO
d
27 LUMO
5 B3LYP Pt Hay-

Wadt Effective Core Potential: ECPPt

LANL2DZ X Z-
4 1 "--Link1--"
372

Vol.,No.2007.11

Standard orientation:
--------------------------------------------------------------------Center
Atomic
Atomic
Coordinates (Angstroms)
Number
Number
Type
X
Y
Z
--------------------------------------------------------------------1
78
0
-0.000006
0.189005
-0.000363
2
17
0
-1.731734
-1.397918
0.000459
3
17
0
1.731902
-1.397802
0.000312
4
7
0
1.595441
1.580739
0.000781
5
7
0
-1.595669
1.580480
0.000540
6
1
0
1.630305
2.173570
0.830389
7
1
0
2.429116
0.981478
0.001876
8
1
0
1.632079
2.173563
-0.828790
9
1
0
-1.630429
2.173985
0.829668
10
1
0
-1.632592
2.172611
-0.829509
11
1
0
-2.429253
0.981094
0.002297
--------------------------------------------------------------------Molecular Orbital Coefficients
26
27
28
29
30
(A)--O
(A)--V
(A)--V
(A)--V
(A)--V
EIGENVALUES --0.20416 -0.03139
0.02618
0.04724
0.11415
1 1
Pt 1S
0.00000
0.00000 -0.00008
0.06956
0.00000
2
2S
0.00003 -0.00002 -0.00090
0.68365
0.00003
3
3PX
-0.00007 -0.01968 -0.00001
0.00000 -0.10182
4
3PY
-0.00001
0.00000
0.00004 -0.08194
0.00000
5
3PZ
0.00000
0.00001 -0.14816 -0.00009
0.00001
6
4PX
0.00004
0.08206
0.00007
0.00000
1.08579
7
4PY
0.00001
0.00000 -0.00030
0.74252 -0.00003
8
4PZ
0.00002 -0.00004
1.05866
0.00097 -0.00009
9
5D 0
0.00006
0.00001
0.00041 -0.31877
0.00000
z
10
5D+1
-0.55151
0.00017
0.00000
0.00002
0.00018
11
5D-1
0.00002
0.00002 -0.06027
0.00017
0.00002
12
5D+2
0.00004 -0.00012 -0.00007
0.06867
0.00000
y
13
5D-2
-0.00001
0.88441
0.00004
0.00003 -0.09388
14 2
Cl 1S
-0.00002 -0.11465
0.00004
0.01428
0.37149
15
2PX
-0.00075 -0.35455
0.00008 -0.05281 -0.01591
16
2PY
-0.00016 -0.25892
0.00021 -0.26258
0.24519
x
17
2PZ
-0.63615
0.00028 -0.31460 -0.00017 -0.00006
18 3
Cl 1S
0.00001
0.11465
0.00003
0.01427 -0.37155
19
2PX
-0.00073 -0.35457 -0.00014
0.05282 -0.01583
20
2PY
0.00002
0.25890
0.00021 -0.26258 -0.24520
21
2PZ
0.63629 -0.00020 -0.31459 -0.00019
0.00009
4
22 4
N 1S
-0.00002
0.05419 -0.000045
0.10352
0.08828
23
2S
0.00013 -0.31336
0.00019 -0.67118 -0.61880
24
2PX
-0.00019
0.27206 -0.00021
0.21845 -0.13012
25
2PY
-0.00013
0.19281 -0.00012
0.02134 -0.03749
26
2PZ
0.01492
0.00031 -0.13536
0.00003
0.00006
1
27 5
N 1S
0.00002 -0.05420 -0.00006
0.10351 -0.08829
28
2S
-0.00009
0.31340
0.00036 -0.67110
0.61888
29
2PX
-0.00015
0.27211
0.00022 -0.21845 -0.13011
30
2PY
0.00010 -0.19278 -0.00012
0.02129
0.03752
31
2PZ
-0.01493 -0.00021 -0.13536
0.00002 -0.00010
3
2
32 6
H 1S
0.03476
0.05370 -0.04994
0.12982
0.20182
33 7
H 1S
0.00003
0.01658 -0.00008
0.11249
0.10687
34 8
H 1S
-0.03484
0.05371
0.04995
0.12991
0.20190
35 9
H 1S
-0.03476 -0.05373 -0.04996
0.12980 -0.20184
36 10 H 1S
0.03486 -0.05369
0.04992
0.12989 -0.20192
37 11 H 1S
-0.00007 -0.01659 -0.00014
0.11248 -0.10687

LUMO

4 B3LYP/LANL2MB

B3LYP LANL2MB
Pt Cl Hay-Wadt
STO-3G
6 LUMO 6a
Standard orientation 4
1s
4 5D2
1 Gaussian d

Vol.,No.2007.11

373

 5
1 d

Gaussian

D0
D1
D1
D2
D2

d2z x y
dzx
dyz
dx y
dxy
2

1 dxy dxy xy
x y dxy x y
dxy
d
d 1/3 N Cl pxpy
pz p xy z
6b

374

Vol.,No.2007.11

 6c
4
5

1
2

2
(a)

x1

2 3
3
(a) (a)

4
y
x

3
(b)

(b) (b)

(c)

(c) (c)

6 LUMO (a) (b)

p
(c) (b)
7 moview 6c
LUMO

7moview LUMO
split valence
diffuse diffuse

Vol.,No.2007.11

375

10.4

a.u.

g03cuto [11]g03cuto
g03cutoGaussian

cisplatin1.log Pt D2
hpc% g03cuto cisplatin1.log 1d-2
> Enter the number of virtual orbital cycle ?
1
5
Molecular Orbital Coefficients
1
2
3
4
5
(A)--O
(A)--O
(A)--O
(A)--O
(A)--O
EIGENVALUES --14.30103 -14.30096 -3.92705 -2.16126 -2.15495
1 1
Pt 1S
-0.00081
0.00000
0.99955
0.00000
0.00042
13
5D-2
-0.00001
0.00252
0.00000 -0.00166
0.00000
6
7
8
9
10
(A)--O
(A)--O
(A)--O
(A)--O
(A)--O
EIGENVALUES --2.11258 -0.95513 -0.95229 -0.70927 -0.70256
1 1
Pt 1S
0.00000 -0.02563
0.00000 -0.04116 -0.00004
13
5D-2
0.00000 -0.00001
0.03611
0.00012 -0.12125
11
12
13
14
15
<< >>
EIGENVALUES -1 1
Pt 1S
13
5D-2
EIGENVALUES -1 1
Pt 1S
13
5D-2
EIGENVALUES -1 1
Pt 1S
13
5D-2
hpc%

21
(A)--O
-0.27744
0.04956
0.00013
26
(A)--O
-0.20416
0.00000
-0.00001
31
(A)--V
0.17341
0.10092
0.00003
36
(A)--V

22
(A)--O
-0.23952
-0.00731
0.00000
27
(A)--V
-0.03139
0.00000
0.88441
32
(A)--V
0.31881
-0.00003
-0.00007
37
(A)--V

23
(A)--O
-0.22456
0.00000
0.04891
28
(A)--V
0.02618
-0.00008
0.00004
33
(A)--V
0.32245
0.00000
0.02880

24
(A)--O
-0.21701
-0.00736
-0.00004
29
(A)--V
0.04724
0.06956
0.00003
34
(A)--V
0.32451
0.00000
0.00018

25
(A)--O
-0.21671
-0.00011
0.00000
30
(A)--V
0.11415
0.00000
-0.09388
35
(A)--V
0.32790
-0.00811
0.00000

8g03cuto D2

376

Vol.,No.2007.11

 g03cuto 8
8 D2
D2 27
d

Pt d
%hpc g03cuto cisplatin1.log 1D
SP... Pt

%hpc g03cuto cisplatin1.log 1

%hpc g03cuto cisplatin1.log 2-3sp

Cl s p

hpc% g03cuto cisplatin1.log 1d,4-5p

Pt d 4 5 N p

g03cuto UHF
a b

[1]

E. R. Scerri J. Chem. Educ. 77, 1492-1494, 2000

[2]

A. Szabo, N. S. Ostlund Modern Quantum Chemistr y: Introduction to Advanced

Electronic Structure Theory, Dover, 1996
1987

[3]

Wolfram Koch, Max C. HolthausenA Chemists Guide to Density Functional Theory, p.

49WILEY-VCH, Weinheim, 2000

[4]

R. Stowasser, R. Hoffmann J. Am. Chem. Soc., 121, 3414-3420, 1999

Vol.,No.2007.11

377

[5]

1986

[6]

1976

[7]

T. S. Albright, J. H. Burdett, M.-H. WhangboOrbital Interactions in Chemistry, John

Wiley & Sons, Inc., 1985

[8]

R. Hof fmann Solids and Sur faces: A Chemical View of Bonding in Extended
Structures, VCH Publishers, Inc., 1988

1993

[9]

GaussView version 4.0, Gaussian Inc. http://www.gaussian.com/gv_plat.htm

[10]

5 328-3342006

[11]

378

Vol.,No.2007.11