Gaussian 03 6

Gaussian 03

Q
Gaussian 03

[1,2]
Q U S 12

kB 1.38054 10

282

23

JK 1T

Vol.,No.2007. 8

2
Qel Qtrans Qrot Qvib
3
Q Qel Qtrans Qrot Qvib

1245

U Eel Etrans Erot Evib

S Sel Strans Srot Svib

6
6
RR 1.987 cal K 1mol

R 8.3145 JK

mol 1

Erot RT

7
U 8

S 9
Erot RT

S Strans Srot Svib

8
9

Eel B3LYP/6-31G
d
3 [3]Eel=

76.408954 a.u.1 a.u. = 627.50955 kcal mol 1 2625.5000 kJ mol 1298.15 K

3.7185 kJ mol 1

10

Evib 11

11

3N 6 3N 5
3 3 6 3

Vol.,No.2007. 8

283

12
vi h 6.6261 10

34

J s 1i

cm 1
c 2.997925 108 m s 1NA 6.02214

1023 mol 1NA kB R 1.987 cal K 1 mol 1 R 8.3145 JK 1 mol 1

11 {} 1/2

d Evib
B3LYP/6-31G
i 1713.53973727.7863 3849.3633 cm 1 298.15 K i 11
1713.5397 cm 1

13

i 22 = 3727.7863 cm 1

14

i 33 3849.3633 cm 1

15

vi 1315 298.15 K

2465.405363.455538.37 K 5 3 [3]
131511

16

SI

Evib 55.576 kJ mol

284

17

Vol.,No.2007. 8

 10

18

18

627.50955 kcal mol 1

SI EtransErotEvib 2625.5000

9 Strans 19

19
M 18.01057 amu T K P
atm Srot 20
20

ABC ABC C2v

2 1
1

C1CiCs

D2D2dD2h

Cv

C2C2vC2h

D3D3dD3h

Dv

C3C3vC3h

D4D4dD4h

Td

12

C4C4vC4h

D6D6dD6h

12

Oh

24

C6C6vC6h

Svib 21

21

Strans 22

Vol.,No.2007. 8

285

22

Srot 20 ABC 23

23

Ixx Ixy 2425

24

25

mi i
xi, yi, zi
i
i Xi, Yi, Zi
24252627

26

27
2
22627

Xi

Yi

Zi

mi Xi

miYi

mi Zi

15.99491

0.000000

0.000000

0.119808

0.000000

0.000000

1.916318

1.00783

0.000000

0.761267

0.479234

0.000000

0.767228

0.482986

1.00783

0.000000

0.761267

0.479234

0.000000

0.767228

0.482986

0.000000

0.000000

0.950345

18.01057

286

Vol.,No.2007. 8

mi Xi2

miYi2

mi Zi2

mi XiYi

miYi Zi

mi Zi Xi

0.000000

0.000000

0.229590

0.000000

0.000000

0.000000

0.000000

0.584065

0.231464

0.000000

0.367682

0.000000

0.000000

0.584065

0.231464

0.000000

0.367682

0.000000

0.000000

1.168130

0.692517

0.000000

0.000000

0.000000

Zi Gaussian Standard
ABC 2 XiYi
orientation 2 262728

28

29

29

30

30

Vol.,No.2007. 8

287

293023 ABC 31

31

20 ABC 32

32

Svib xi vi/T 33
33
3 xiexp xi
3 B3LYP/6-31G
d
e
i

/cm

xi

xi

8.26899

2.563448 10

xi

1713.5397

3727.7863

17.9891

1.539708 10

3849.3633

18.5758

8.563310 10

i 1

34

i 2

35

i 3

288

Vol.,No.2007. 8

36

3 i 1 1713.5397 cm 1
1 298.15 K Svib

37

37

5 3 [3]

32
Gibbs 22
3738

38

39

39

3839

40

Vol.,No.2007. 8

289

373 K1 41
Gaussian
8.1
[4]

2H2O H2O2

41

G Kp 42
G GH2O
2GH2O
2

42

%NPROC=8
%CHK=Water2RHF.chk
#P RHF/6-31G(d) OPT=GDIIS IOP(2/16=1)
Water Dimer
0 1
1H
2O
1
3H
2
4X
3
5O
3
6H
5
7H
5
R1
R2
R3
R4
R5
T1
T2
T3
T4
D1
D2
D3

R1
R2
10.0
R3
R4
R5

GDIIS

1
2
4
3
3

0.968
0.969
2.0
0.968
0.969
105.0
90.0
109.0
109.0
180.0
60.0
-60.0

T1
90.0
T2
T3
T4

1
2
4
4

180.0
D1
D2
D3

H1
O2

H3
X4

O5

H7

H6

--Link1-%NPROC=8
%MEM=10MW
%CHK=Water2RHF.chk
#P RHF/6-31G(d) FREQ=NORAMAN
GEOM=CHECKPOINT GUESS=CHECKPOINT NOSYMM

Water Dimer
0 1

1 RHF/6-31G
d
Z-

290

Vol.,No.2007. 8


40

Z-
Z- 1
B3LYP/6-31G
d
RHF
GDIIS
O H- - -O Z-
X 180 5 CH3Cl-F

Z-
12 2 B3LYP

1
B3LYP/6-31G
d 2
%NPROC=8
%CHK=Water2.chk
#P B3LYP/6-31G(d) OPT=GDIIS IOP(2/16=1)

Water Dimer
0 1
H
O
H
O
H
H

-1.591178
-1.492445
-0.553562
1.382908
1.510610
1.510433

-0.000069
-0.000148
-0.000048
0.000136
-0.756321
0.756535

-1.333710
-0.392151
-0.235844
0.359161
0.916679
0.916798

--Link1-%NPROC=8
%CHK=Water2.chk

#P B3LYP/6-31G(d) OPT=(GDIIS,READFC) IOP(2/16=1) INT(GRID=ULTRAFINE)

GEOM=CHECKPOINT GUESS=CHECKPOINT
Water Dimer

0 1
--Link1-%NPROC=8
%MEM=10MW
%CHK=Water2.chk
#P B3LYP/6-31G(d) FREQ=NORAMAN IOP(2/16=1) INT(GRID=ULTRAFINE)
GEOM=CHECKPOINT GUESS=CHECKPOINT

Water Dimer
0 1

2 B3LYP/6-31G
d

RHF/6-31G
d

Vol.,No.2007. 8

291


4
[5]
B3LYP/6-31G
d 17
(a)

%NPROC=8
%CHK=Water2.chk

#P B3LYP/6-31G(d) OPT=(GDIIS,READFC) IOP(2/16=1) INT(GRID=ULTRAFINE)

NOSYMM GUESS=CHECKPOINT

Water Dimer
0 1

H
O
H
O
H
H

1.961883
1.453075
0.522206
-1.396522
-1.166945
-1.769563

0.702207
-0.121138
0.175325
0.127951
-0.387026
-0.545015

0.373001
-0.006491
-0.281754
-0.013164
0.842875
-0.685186

--Link1-%NPROC=8
%MEM=10MW
%CHK=Water2.chk
#P B3LYP/6-31G(d) FREQ=NORAMAN IOP(2/16=1) INT(GRID=ULTRAFINE)
GEOM=CHECKPOINT GUESS=CHECKPOINT NOSYMM
Water Dimer
0 1

(b)

%NPROC=8
%CHK=Water2.chk

#P B3LYP/6-31G(d) OPT=(GDIIS,READFC) IOP(2/16=1) INT(GRID=ULTRAFINE)

GEOM=CHECKPOINT GUESS=CHECKPOINT
Water Dimer

0 1
--Link1-%NPROC=8
%MEM=10MW
%CHK=Water2.chk

#P B3LYP/6-31G(d) FREQ=NORAMAN IOP(2/16=1) INT(GRID=ULTRAFINE)

GEOM=CHECKPOINT GUESS=CHECKPOINT

Water Dimer
0 1

%Chk=Water2.chk
# FREQ=(READISO,READFC) GEOM=ALLCHECKPOINT GUESS=CHECKPOINT
(K)

(atm)

373.0 1.0 0.9804

1

16
1
16

1
1

(c)

3 B3LYP/6-31Gd
a 2

b
a

c
b 373 K b

292

Vol.,No.2007. 8

 RHF

0.3

MOLCAT[6]

23

3
3
MOLCAT RHF/6-31G
d B3LYP/6-31G
d
4

0.947

105.4
0.952

2.660

2.026

0.969
0.948
105.8

0.973
2.663

172.4

RHF/6-31G(d) : 115.5 cm1

0.969
0.973
103.8

B3LYP/6-31G(d) : 34.0 cm1

4MOLCAT
10 kcal mol

BSSE [7]BSSE

BSSE BSSE
6-311+G
2df,2p

BSSE counterpoise [8,9]

//B3LYP/6-31Gd
4 B3LYP/6-31G
d B3LYP/6-311+G
2df,2p
B3LYP/6-31G
d B3LYP/6-

311+G2df,2p//B3LYP/6-31Gd//
B3LYP/6-31G
d 4.54

kcal mol 1 BSSE

H2O Zero-point correction Thermal correction 5 3
Sum

of electronic and thermal ...

4 1 298.15 KH 1.31

kcal mol 1 Gibbs G 4.69 kcal mol 1

Vol.,No.2007. 8

293

 4298.15 K 2H2O (H2O)2

a

6-31G(d)

H2O

2H2O

2H2O (H2O)2

(H2O)2

(a.u.)

(kcal mol1)

76.408954 152.817908 152.830336

0.012428

7.80

76.462412 152.924823 152.930022

0.005199

3.26

6-311+G(2df,2p)

(E)

Thermal correction
to Energy

(1)

0.024000

0.048000

0.052058

0.004058

2.55

Thermal correction
to Enthalpy

(2)

0.024944

0.049888

0.053002

0.003114

1.95

Thermal correction
to Gibbs Free
Energy

(3)

0.003498

0.006996

0.019664

0.012668

7.95

(E)(1) 76.438412 152.876823 152.877964

0.001141

0.72

(E)(2) 76.437468 152.874935 152.877020

0.002085

1.31

Gibbs

(E)(3) 76.458914 152.917827 152.910358

0.007469

4.69

a.u.

4243
43

298.15 K 10000 4

373 K
5

34180206 296

cm 1
H 373 1.19 kcal mol 1 Gibbs G 373 6.08 kcal mol

Kp 3.5 10

373 K H 373 3.6 0.5 kcal mol 1

//B3LYP/6-31Gd 3
B3LYP/6-311+G
2df,2p
//RHF/6-31Gd
RHF/6-311+G
2df,2p
H 373 2.1 kcal mol 1 G 373 4.6 kcal mol 1Kp
4.3 10 4 [10]B3LYP
van der Waals

294

Vol.,No.2007. 8

 5373 K 2H2O (H2O)2

a

H2O

2H2O

(H2O)2

2H2O (H2O)2
(a.u.)

(kcal mol1)

76.462412

152.924823

152.930022

0.005199

3.26

Thermal correction to
Energy

0.024306

0.048612

0.053094

0.004482

2.81

Thermal correction to
Enthalpy

0.025488

0.050976

0.054275

0.003299

2.07

Thermal correction to
Gibbs Free Energy

0.002412

0.004824

0.010058

0.014882

9.34

76.438106

152.876211

152.876928

0.000717

0.45

76.436924

152.873847

152.875747

0.001900

1.19

Gibbs

76.464824

152.929647

152.919964

0.009683

6.08

6-311+G(2df,2p)

a.u. 0.9804

MP2 post-SCF
H 373
H 298

d
B3LYP/6-31G

2df,2p
Gibbs B3LYP/6-311+G

//B3LYP/6-31Gd RHF/6-311+G2df,2p//RHF/6-31Gd
BSSE B3LYP

Vol.,No.2007. 8

295

[1]

J. H. Knox

1974

[2]

http://www.gaussian.com/g_whitepap/white_pap.htm Thermochemistr y in
Gaussian

[3]

Gaussian 03 5
Vol. 6No. 2190-2072007

[4]

J. B. Foresman and . Frisch

Gaussian Inc., Pittsburgh, 1998

[5]

Gaussian 03 4
Vol. 6No. 145-592007

[6]

Y. Tsutsui and H. Wasada, Chem. Lett., 5171995. http://www2.itc.nagoya-u.ac.jp/

sys_riyou/hpc/index.htm MOLCAT

[7]

Gaussian 03 3
Vol. 5No. 4335-3492006

[8]

6
Gaussian98 Vol. 31No. 3

195-2132000
[9]

N. R. Kestner, J. E. CombarizaReviews in Computational Chemistry, 13, 99-1321999

[10]

RHF/6-31Gd HF/6-31Fd
0.9135 [4] 64
http://srdata.nist.gov/cccbdb/ . B. 4. a.

296

Vol.,No.2007. 8