P 和佐田.indd

Gaussian 03 Q Gaussian 03 [1,2] Q U S 1 2 k B 1.38054 10 23 JK 1 T

1 2 Q el Q trans Q rot Q vib 3 Q Q el Q trans Q rot Q vib 1 24 5 U E el E trans E rot E vib S S el S trans S rot S vib 6 3 4 5 6 R R 1.987 cal K 1 mol 1 R 8.3145 JK 1 mol 1 2 E rot RT 7 U 8 S 9 E rot RT 8 S S trans S rot S vib 9 E el B3LYP/6-31G d 3 [3] E el = 76.408954 a.u. 1 a.u. = 627.50955 kcal mol 1 2625.5000 kj mol 1 298.15 K 3.7185 kj mol 1 10 E vib 11 11 3N 6 3N 5 3 3 6 3

12 i v h 6.6261 10 34 J s 1 i cm 1 c 2.997925 10 8 m s 1 N A 6.02214 10 23 mol 1 N A k B R 1.987 cal K 1 mol 1 R 8.3145 JK 1 mol 1 11 { } 1/2 B3LYP/6-31G d E vib i 1713.5397 3727.7863 3849.3633 cm 1 298.15 K i 1 1 1713.5397 cm 1 13 i 2 2 = 3727.7863 cm 1 14 i 3 3 3849.3633 cm 1 15 v i 13 15 298.15 K 2465.40 5363.45 5538.37 K 5 3 [3] 13 1511 16 SI E vib 55.576 kj mol 1 17

10 3 18 18 627.50955 kcal mol 1 SI E trans E rot E vib 2625.5000 9 S trans 19 19 M 18.01057 amu T K P atm S rot 20 20 ABC A B C C 2v 2 1 C 1 C i C s 1 D 2 D 2d D 2h 4 C v 1 C 2 C 2v C 2h 2 D 3 D 3d D 3h 6 D v 2 C 3 C 3v C 3h 3 D 4 D 4d D 4h 8 T d 12 C 4 C 4v C 4h 4 D 6 D 6d D 6h 12 O h 24 C 6 C 6v C 6h 6 S vib 21 21 S trans 22

22 S rot 20 ABC 23 23 I xx I xy 24 25 24 25 m i i x i, y i, z i i i X i, Y i, Z i 24 25 26 27 26 27 2 X i Y i Z i m i X i m i Y i m i Z i O 15.99491 0.000000 0.000000 0.119808 0.000000 0.00000.916318 H 1.00783 0.000000 0.761267 0.479234 0.000000 0.767228 0.482986 H 1.00783 0.000000 0.761267 0.479234 0.000000 0.767228 0.482986 18.01057 0.000000 0.000000 0.950345

2 m i X i 2 m i Y i 2 m i Z i m i X i Y i m i Y i Z i m i Z i X i O 0.000000 0.000000 0.229590 0.000000 0.000000 0.000000 H 0.000000 0.584065 0.231464 0.000000 0.367682 0.000000 H 0.000000 0.584065 0.231464 0.000000 0.367682 0.000000 0.00000.168130 0.692517 0.000000 0.000000 0.000000 ABC 2 X i Y i Z i Gaussian Standard orientation 2 26 27 28 28 29 29 30 30

29 30 23 ABC 31 31 20 ABC 32 32 S vib x i vi /T 33 33 3 x i exp x i e xi i /cm 1 x i e xi 1 1713.5397 8.26899 2.563448 10 4 2 3727.7863 17.9891 1.539708 10 8 3 3849.3633 18.5758 8.563310 10 9 i 1 34 i 2 35 i 3

36 3 i 1 1713.5397 cm 1 1 298.15 K S vib 37 37 5 3 [3] Gibbs 2232 37 38 38 39 39 38 39 40

373 K 1 41 Gaussian 8.1 [4] 2H 2 O H 2 O 2 41 G K p 42 G G H 2 O 2 2G H 2 O 42 %CHK=Water2RHF.chk #P RHF/6-31G(d) OPT=GDIIS IOP(2/16=1) 構造最適化 GDIIS 法で構造最適化 対称性が変化しても計算を続行す るためのオプション 1 H 2 O 1 R1 3 H 2 R2 1 T1 4 X 3 10.0 2 90. 180.0 ダミー原子 5 O 3 R3 4 T2 2 D1 6 H 5 R4 3 T3 4 D2 7 H 5 R5 3 T4 4 D3 R1 0.968 R2 R3 0.969 2.0 H 1 R4 0.968 R5 0.969 T1 105.0 T2 90.0 T3 109.0 T4 109.0 D1 180.0 D2 60.0 D3-60.0 --Link1-- %MEM=10MW %CHK=Water2RHF.chk O 2 H 3 X 4 O 5 #P RHF/6-31G(d) FREQ=NORAMAN GEOM=CHECKPOINT GUESS=CHECKPOINT NOSYMM 振動解析 H 6 H 7

40 Z- Z- 1 B3LYP/6-31G d RHF GDIIS O H---O Z- X 180 5 CH 3 Cl-F Z- 12 2 B3LYP 1 B3LYP/6-31G d 2 %CHK=Water2.chk #P B3LYP/6-31G(d) OPT=GDIIS IOP(2/16=1) 粗いグリッドで構造最適化 H -1.591178-0.000069-1.333710 O -1.492445-0.000148-0.392151 H -0.553562-0.000048-0.235844 O 1.382908 0.000136 0.359161 H 1.510610-0.756321 0.916679 H 1.510433 0.756535 0.916798 --Link1-- %CHK=Water2.chk 細かいグリッドで構造最適化 #P B3LYP/6-31G(d) OPT=(GDIIS,READFC) IOP(2/16=1) INT(GRID=ULTRAFINE) GEOM=CHECKPOINT GUESS=CHECKPOINT チェックポイントファイルから内部座標に依存した力の定数を読み込む --Link1-- %MEM=10MW %CHK=Water2.chk #P B3LYP/6-31G(d) FREQ=NORAMAN IOP(2/16=1) INT(GRID=ULTRAFINE) GEOM=CHECKPOINT GUESS=CHECKPOINT 振動解析

4 [5] B3LYP/6-31G d 17 %CHK=Water2.chk (a) #P B3LYP/6-31G(d) OPT=(GDIIS,READFC) IOP(2/16=1) INT(GRID=ULTRAFINE) NOSYMM GUESS=CHECKPOINT 重心を中心とした座標系に回転しない虚数振動モードの方向に変位した座標 H 1.961883 0.702207 0.373001 O 1.453075-0.121138-0.006491 H 0.522206 0.175325-0.281754 O -1.396522 0.127951-0.013164 H -1.166945-0.387026 0.842875 H -1.769563-0.545015-0.685186 --Link1-- %MEM=10MW %CHK=Water2.chk #P B3LYP/6-31G(d) FREQ=NORAMAN IOP(2/16=1) INT(GRID=ULTRAFINE) GEOM=CHECKPOINT GUESS=CHECKPOINT NOSYMM %CHK=Water2.chk (b) #P B3LYP/6-31G(d) OPT=(GDIIS,READFC) IOP(2/16=1) INT(GRID=ULTRAFINE) GEOM=CHECKPOINT GUESS=CHECKPOINT --Link1-- %MEM=10MW %CHK=Water2.chk チェックポイントファイルから振動解析計算結果の力の定数を読み込む #P B3LYP/6-31G(d) FREQ=NORAMAN IOP(2/16=1) INT(GRID=ULTRAFINE) GEOM=CHECKPOINT GUESS=CHECKPOINT 振動解析 %Chk=Water2.chk # FREQ=(READISO,READFC) GEOM=ALLCHECKPOINT GUESS=CHECKPOINT 温度 (K) 圧力 (atm) スケーリングファクター 373..0 0.9804 1 デフォルト値を変更しない場合であっても 16 水素の質量数スケーリングファクター以外は省略できない 1 16 酸素の質量数 1 1 (c)

RHF 0.3 MOLCAT[6] 23 3 3 MOLCAT RHF/6-31G d B3LYP/6-31G d 4 0.947 Å 105.4 º 0.952 Å 172.4 º 2.026 Å 0.948 Å 105.8 º 0.969 Å 2.660 Å 0.973 Å 0.969 Å 2.663 Å 103.8 º 0.973 Å RHF/6-31G(d) : 115.5 cm 1 B3LYP/6-31G(d) : 34.0 cm 1 10 kcal mol 1 BSSE [7] BSSE BSSE BSSE 6-311+G 2df,2p BSSE counterpoise [8,9] 4 B3LYP/6-31G d B3LYP/6-311+G 2df,2p //B3LYP/6-31G d B3LYP/6-31G d B3LYP/6-311+G 2df,2p //B3LYP/6-31G d// B3LYP/6-31G d 4.54 kcal mol 1 BSSE H 2 O 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

6-31G(d) 6-311+G(2df,2p) Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy 2H 2 O (H 2 O) 2 H 2 O 2H 2 O (H 2 O) 2 (a.u.) (kcal mol 1 ) 76.408954 152.817908 152.830336 0.012428 7.80 (E) 76.462412 152.924823 152.930022 0.005199 3.26 (1) 0.024000 0.048000 0.052058 0.004058 2.55 (2) 0.024944 0.049888 0.053002 0.003114 1.95 (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 a.u. 4243 43 298.15 K 10000 4 373 K 5 34 180 206 296 cm 1 H 373 1.19 kcal mol 1 Gibbs G 373 6.08 kcal mol 1 K p 3.5 10 5 4 373 K H 373 3.6 0.5 kcal mol 1 B3LYP/6-311+G 2df,2p //B3LYP/6-31G d 3 RHF/6-311+G 2df,2p //RHF/6-31G d H 373 2.1 kcal mol 1 G 373 4.6 kcal mol 1 K p 4.3 10 4 [10] B3LYP van der Waals

2H 2 O (H 2 O) 2 H 2 O 2H 2 O (H 2 O) 2 (a.u.) (kcal mol 1 ) 6-311+G(2df,2p) 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 Thermal correction to Gibbs Free Energy 0.025488 0.050976 0.054275 0.003299 2.07 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 a a.u. 0.9804 MP2 post-scf H 373 H 298 B3LYP/6-31G d Gibbs B3LYP/6-311+G 2df,2p //B3LYP/6-31G d RHF/6-311+G 2df,2p //RHF/6-31G d BSSE B3LYP

[1] J. H. Knox 1974 [2] http://www.gaussian.com/g_whitepap/white_pap.htm Thermochemistr y in Gaussian [3] Gaussian 03 5 Vol. 6 No. 2 190-207 2007 [4] J. B. Foresman and Æ. Frisch Gaussian Inc., Pittsburgh, 1998 [5] Gaussian 03 4 Vol. 6 No. 1 45-59 2007 [6] Y. Tsutsui and H. Wasada, Chem. Lett., 517 1995. http://www2.itc.nagoya-u.ac.jp/ sys_riyou/hpc/index.htm MOLCAT [7] Gaussian 03 3 Vol. 5 No. 4 335-349 2006 [8] 6 Gaussian98 Vol. 31 No. 3 195-213 2000 [9] N. R. Kestner, J. E. Combariza Reviews in Computational Chemistry, 13, 99-132 1999 [10] RHF/6-31G d HF/6-31F d 0.9135 [4] 64 http://srdata.nist.gov/cccbdb/. B. 4. a.