P 和佐田.indd

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

2 1 2 Q el Q trans Q rot Q vib 3 Q Q el Q trans Q rot Q vib U E el E trans E rot E vib S S el S trans S rot S vib R R cal K 1 mol 1 R 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 = a.u. 1 a.u. = kcal mol kj mol K kj mol 1 10 E vib N 6 3N

3 12 i v h J s 1 i cm 1 c m s 1 N A mol 1 N A k B R cal K 1 mol 1 R JK 1 mol 1 11 { } 1/2 B3LYP/6-31G d E vib i cm K i cm 1 13 i 2 2 = cm 1 14 i cm 1 15 v i K K 5 3 [3] SI E vib kj mol 1 17

4 kcal mol 1 SI E trans E rot E vib S trans M amu T K P atm S rot 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 S trans 22

5 22 S rot 20 ABC I xx I xy m i i x i, y i, z i i i X i, Y i, Z i X i Y i Z i m i X i m i Y i m i Z i O H H

6 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 H H ABC 2 X i Y i Z i Gaussian Standard orientation

7 ABC ABC S vib x i vi /T x i exp x i e xi i /cm 1 x i e xi i 1 34 i 2 35 i 3

8 36 3 i cm K S vib [3] Gibbs

9 373 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 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 R R2 R H 1 R R T T T T D D D 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

10 40 Z- Z- 1 B3LYP/6-31G d RHF GDIIS O H---O Z- X CH 3 Cl-F Z 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 O H O H H 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

11 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 O H O H H 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)

12 RHF 0.3 MOLCAT[6] MOLCAT RHF/6-31G d B3LYP/6-31G d Å º Å º Å Å º Å Å Å Å Å º Å RHF/6-31G(d) : cm 1 B3LYP/6-31G(d) : 34.0 cm 1 10 kcal mol 1 BSSE [7] BSSE BSSE BSSE 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 KH 1.31 kcal mol 1 Gibbs G 4.69 kcal mol 1

13 6-31G(d) 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 ) (E) (1) (2) (3) (E) (1) (E) (2) Gibbs (E) (3) a a.u K K cm 1 H kcal mol 1 Gibbs G kcal mol 1 K p K H 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 kcal mol 1 G kcal mol 1 K p [10] B3LYP van der Waals

14 2H 2 O (H 2 O) 2 H 2 O 2H 2 O (H 2 O) 2 (a.u.) (kcal mol 1 ) G(2df,2p) Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Gibbs a a.u 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

15 [1] J. H. Knox 1974 [2] Thermochemistr y in Gaussian [3] Gaussian 03 5 Vol. 6 No [4] J. B. Foresman and Æ. Frisch Gaussian Inc., Pittsburgh, 1998 [5] Gaussian 03 4 Vol. 6 No [6] Y. Tsutsui and H. Wasada, Chem. Lett., sys_riyou/hpc/index.htm MOLCAT [7] Gaussian 03 3 Vol. 5 No [8] 6 Gaussian98 Vol. 31 No [9] N. R. Kestner, J. E. Combariza Reviews in Computational Chemistry, 13, [10] RHF/6-31G d HF/6-31F d [4] 64 B. 4. a.

P 和佐田.indd

P 和佐田.indd B3LYP/6-31G* X HGS MOL-TALOU [1] 1 2-4 II CS Chem Office [2] Molecular Dynamics 1 ChemDraw 2 3 Chem 3D 4 Gaussian Input X 28 27 12 13 26 11 29 14 10 15 25 2 9 27 2 21 7 3 43 7 3 5 Cu 41 Cu 4 10 22 28 H