南赢8 6.2 量子化学计算（基本概念)6.2.1 基组 Basis SetXnm = N,R,(S,r)Ym(0,p)Slater函数使用双，基组数目加一倍，效果更好R,(5,r)= rn- exp(-Gr)Xnlm = N,Rn, (α,r)Ym(0,d)Gaussian函数Rn. (α,r)=r"g- exp(-αr2)简缩Gauss基组7(2 / )"22/43Ed,a(2/+3)/4 exp(-ak@)x>(21 + 1)!k=l11111111111111111《量子化学》第六章计算化学
《量子化学》第六章 计算化学 §6.2 量子化学计算 (基本概念) 6.2.1 基组 Basis Set Slater 函数 1 (,) (,) ( , ) exp( ) nlm s n lm n n NR rY R rr r 使用双，基组数目 加一倍，效果更好 Gaussian 函数 1 2 (,) (,) ( , ) exp( ) g g g g n lm g n lm n n N R rY R rr r 简缩Gauss基组 1/2 1/2 2 3 (2 3)/4 2 1 2/ 2 ( ) ( , ) exp( ) (2 1)! l K l l nlm CGTO lm k k k k rY d a ar l 11111111111111111
厂1.极小基组STO-nG，每一个STO用n个GTO线性组合n=2~6,STO-3G可用于非常大的分子定性结果。H~Xc20.0300.6厂0.0250.5STO0.020STO-3G0.0150.40.0100.30.0050.20.00020.10.02013546r/a0.5~4(a），STO与STO-3G吻合较好11111111111111111《量子化学》第六章计算化学
《量子化学》第六章 计算化学 1. 极小基组,STO–nG, 每一个STO用n个GTO线性组合, n=2~6, STO–3G 可用于非常大的分子定性结果。H~Xe 0123456 0.0 0.1 0.2 0.3 0.4 0.5 0.6 345678 0.000 0.005 0.010 0.015 0.020 0.025 0.030 STO STO-3G r/a0 0.5~4(a0) ，STO与STO-3G吻合较好 11111111111111111
UNBASIS="STO-2G"南-a,rIsTO-2G =C,e-αp?RHO+(S21.00R1C1.30975638(a,)0.430128498(C)0.678913531(C)0.233135974(a)****BASIS="STO-3G"-Qa-α2-QR+CIsTO-3G=C,e+eeHoS31.003.425250910.1543289700.6239137300.5353281400.1688554000.444634540★**★BASIS="STO-3G"00S31.00130.7093200.15432897023.80886100.5353281406.443608300.444634540SP31.005.03315130(a-0.099967230(C)0.155916270(C2p)1.169596100.3995128300.6076837200.3803890000.7001154700.391957390★***★11111111111111111《量子化学》第六章计算化学
《量子化学》第六章 计算化学 BASIS="STO-2G" H 0 S 2 1.00 1.30975638(1) 0.430128498(C1) 0.233135974( 2) 0.678913531(C2) **** 2 2 2 1 12 2 r r GSTO eCeCR BASIS="STO-3G" O 0 S 3 1.00 130.709320 0.154328970 23.8088610 0.535328140 6.44360830 0.444634540 SP 3 1.00 5.03315130(sp) -0.099967230(C2s) 0.155916270(C2p) 1.16959610 0.399512830 0.607683720 0.380389000 0.700115470 0.391957390 **** BASIS="STO-3G" H 0 S 3 1.00 3.42525091 0.154328970 0.623913730 0.535328140 0.168855400 0.444634540 **** 2 3 2 2 2 1 13 2 3 r r r GSTO eCeCeCR 11111111111111111
UNI南鳯BASIS="STO-3G"CIOS31.0099601.3456140.154328967109.5358540.53532814229.64467690.444634542SP 3 1.0038.9604189-0.999672292E-010.1559162759.053563480.3995128260.6076837192.944499830.7001154690.391957393BASIS="STO-3G"SP31.00BRO2.12938649-0.2196203690.105876043E-01S31.000.5940934270.2255954340.5951670052629.997470.1543289670.9003984260.4620010120.2325241410.535328142479.057322*★+129.6516070.444634542SP31.00219.835026-0.999672292E-010.15591627551.08493220.3995128260.60768371916.61440550.7001154690.391957393SP31.0019.5017311-0.2277635020.495151120E-025.948649580.2175436040.5777664692.295173940.4846460370.916676961D31.0019.50173110.2197679515.948649580.6555473632.295173940.286573259SP31.001.39603749-0.308844122-0.1215468600.5152256320.196064117E-010.5715227600.2275290711.131034440.549894947*★*★11111111111111111《量子化学》第六章计算化学
《量子化学》第六章 计算化学 BASIS="STO-3G" Cl 0 S 3 1.00 601.345614 0.154328967 109.535854 0.535328142 29.6446769 0.444634542 SP 3 1.00 38.9604189 -0.999672292E-01 0.155916275 9.05356348 0.399512826 0.607683719 2.94449983 0.700115469 0.391957393 SP 3 1.00 2.12938649 -0.219620369 0.105876043E-01 0.594093427 0.225595434 0.595167005 0.232524141 0.900398426 0.462001012 **** BASIS="STO-3G" BR 0 S 3 1.00 2629.99747 0.154328967 479.057322 0.535328142 129.651607 0.444634542 SP 3 1.00 219.835026 -0.999672292E-01 0.155916275 51.0849322 0.399512826 0.607683719 16.6144055 0.700115469 0.391957393 SP 3 1.00 19.5017311 -0.227763502 0.495151120E-02 5.94864958 0.217543604 0.577766469 2.29517394 0.916676961 0.484646037 D 3 1.00 19.5017311 0.219767951 5.94864958 0.655547363 2.29517394 0.286573259 SP 3 1.00 1.39603749 -0.308844122 -0.121546860 0.515225632 0.196064117E-01 0.571522760 0.227529071 1.13103444 0.549894947 **** 11111111111111111
南凰2.双和多基组(double-andmultiple-basis)对每个原子轨道采用2个或更多的基函数3.分裂价基（split-valence或valence-multiple）N-31G：价轨道双简缩基组，内层轨道用N个GTO，每个价层轨道用两个STO(双)表示，STO-3G和STO-1G。由Pople提出，最常用基组，适合有机分子。3-21G(H~Cs)有机分子定性结果6-31G(H~Ar)有机分子定量结果6-311G（H~Kr)有机分子定量结果（三L)BASIS="6-31G0.S61.005484.671700.183110000E-02825.2349500.139501000E-010.684451000E-01188.04696052.96450000.23271430016.89757000.4701930005.799635300.358520900SP 3 1.000.708743000E-0115.5396160-0.1107775003.599933600.1480263000.3397528000.7271586001.013761801.13076700SP 11.000.2700058001.000000001.00000000tt11111111111111111《量子化学》第六章计草化学
《量子化学》第六章 计算化学 2. 双 和多 基组(double- and multiple- basis) 对每个原子轨道采用 2个或更多的基函数 3. 分裂价基(split-valence 或valence-multiple ) N–31G：价轨道双 简缩基组，内层轨道用 N 个GTO，每个价层 轨道用两个STO( 双 )表示，STO–3G 和STO–1G。由Pople提出，最常用 基组，适合有机分子。 3-21G (H~Cs)有机分子定性结果 6-31G (H~Ar)有机分子定量结果 6-311G (H~Kr)有机分子定量结果 ( 三 ) BASIS="6-31G " O 0 S 6 1.00 5484.67170 0.183110000E-02 825.234950 0.139501000E-01 188.046960 0.684451000E-01 52.9645000 0.232714300 16.8975700 0.470193000 5.79963530 0.358520900 SP 3 1.00 15.5396160 -0.110777500 0.708743000E-01 3.59993360 -0.148026300 0.339752800 1.01376180 1.13076700 0.727158600 SP 1 1.00 0.270005800 1.00000000 1.00000000 **** 11111111111111111