武汉大学分子模拟实验作业第十一章光谱模拟.docx
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武汉大学分子模拟实验作业第十一章光谱模拟
11-4-1
PM3
HF/6-31G（d）
B3LYP/6-31G（d）
MP2/6-31G（d）
拉曼光谱模拟（甲烷分子的Raman光谱HF/6-31G（d））
------------GAMESSInterface------------
Model:
Untitled-1
GAMESSJob:
Minimize（Energy/Geometry）RHF/6-31G（d）
Finish@energy=-25222.830226Kcal/Mol（-40.195172Hartrees）
------------------------------------------
PUNCH中Hessian数据
$HESS
ENERGYIS-40.1951717590E（NUC）IS13.5110377539
116.21632110E-011.74972133E-06-1.29287921E-06-5.76377714E-02-2.38972813E-03
12-1.47162917E-03-5.76204512E-02-1.30816035E-031.05566661E-03-2.52268416E-01
131.06162551E-021.38219883E-01-2.54104975E-01-6.92012964E-03-1.37802624E-01
211.74972133E-066.21813073E-01-6.80057005E-06-2.38974905E-03-2.70385412E-01
22-1.31031330E-01-1.30813608E-03-2.35352893E-011.43430231E-011.06164001E-02
23-5.82046816E-02-7.53867767E-03-6.92025131E-03-5.78695874E-02-4.85335621E-03
31-1.29287921E-06-6.80057005E-066.21714867E-01-1.47162756E-03-1.31030042E-01
32-1.38307089E-011.05563707E-031.43428877E-01-1.73357682E-011.38221844E-01
33-7.53868172E-03-1.55776362E-01-1.37804561E-01-4.85333910E-03-1.54273139E-01
41-5.76377714E-02-2.38974905E-03-1.47162756E-035.41600392E-022.65410072E-03
421.63446608E-03-1.19851512E-03-1.47447954E-04-1.07029186E-042.65783682E-03
432.85870569E-021.52166565E-022.01830720E-03-2.87039647E-02-1.52724699E-02
51-2.38972813E-03-2.70385412E-01-1.31030042E-012.65410072E-032.90441750E-01
521.45528290E-01-2.49548353E-04-2.26823271E-02-1.62531622E-029.74616987E-04
531.02976927E-037.28948034E-04-9.89454108E-041.59604004E-031.02564638E-03
61-1.47162917E-03-1.31031330E-01-1.38307089E-011.63446608E-031.45528290E-01
621.43752523E-012.51428487E-042.12611128E-021.65411509E-02-1.99823320E-03
63-1.79400752E-02-1.10299914E-021.58396169E-03-1.78183387E-02-1.09567585E-02
71-5.76204512E-02-1.30813608E-031.05563707E-03-1.19851512E-03-2.49548353E-04
722.51428487E-045.41408205E-021.45283744E-03-1.17240537E-032.12099157E-03
73-2.64321242E-021.86833027E-022.55705097E-032.65369708E-02-1.88179612E-02
81-1.30816035E-03-2.35352893E-011.43428877E-01-1.47447954E-04-2.26823271E-02
822.12611128E-021.45283744E-032.51533076E-01-1.59298584E-01-1.20048372E-03
833.51560419E-03-2.87146434E-031.20324961E-032.98642641E-03-2.51964271E-03
911.05566661E-031.43430231E-01-1.73357682E-01-1.07029186E-04-1.62531622E-02
921.65411509E-02-1.17240537E-03-1.59298584E-011.82681165E-01-1.53861599E-03
931.61487816E-02-1.29789241E-021.76238632E-031.59730755E-02-1.28858710E-02
101-2.52268416E-011.06164001E-021.38221844E-012.65783682E-039.74616987E-04
102-1.99823320E-032.12099157E-03-1.20048372E-03-1.53861599E-032.70331804E-01
103-1.17914498E-02-1.53520349E-01-2.28423634E-021.40094028E-031.88356223E-02
1111.06162551E-02-5.82046816E-02-7.53868172E-032.85870569E-021.02976927E-03
112-1.79400752E-02-2.64321242E-023.51560419E-031.61487816E-02-1.17914498E-02
1135.47857482E-028.37323133E-03-9.79713937E-04-1.12654252E-039.56718493E-04
1211.38219883E-01-7.53867767E-03-1.55776362E-011.52166565E-027.28948034E-04
122-1.10299914E-021.86833027E-02-2.87146434E-03-1.29789241E-02-1.53520349E-01
1238.37323133E-031.63158934E-01-1.85991465E-021.30795071E-031.66262094E-02
131-2.54104975E-01-6.92025131E-03-1.37804561E-012.01830720E-03-9.89454108E-04
1321.58396169E-032.55705097E-031.20324961E-031.76238632E-03-2.28423634E-02
133-9.79713937E-04-1.85991465E-022.72371836E-017.68616361E-031.53057090E-01
141-6.92012964E-03-5.78695874E-02-4.85333910E-03-2.87039647E-021.59604004E-03
142-1.78183387E-022.65369708E-022.98642641E-031.59730755E-021.40094028E-03
143-1.12654252E-031.30795071E-037.68616361E-035.44135606E-025.39063125E-03
151-1.37802624E-01-4.85335621E-03-1.54273139E-01-1.52724699E-021.02564638E-03
152-1.09567585E-02-1.88179612E-02-2.51964271E-03-1.28858710E-021.88356223E-02
1539.56718493E-041.66262094E-021.53057090E-015.39063125E-031.61489425E-01
$END
11-4-2
1.利用GAMESS程序HF/6-31G（d）理论水平优化基态
TotalEnergy=-118450.03822Kcal/Mol
2.手动修改输入方式，其中NSTATE=5
甲酸分子（HCOOH）分子的5个单重态的垂直激发能
CI-SINGLESEXCITATIONENERGIES
STATEHARTREEEVKCAL/MOLCM-1
1A0.22862676966.2213143.465550177.78
1A0.36008630649.7984225.957679029.81
1A0.372043231610.1238233.460781654.05
1A0.403664612110.9843253.303488594.14
1A0.449425760612.2295282.019098637.55
因此，5个单重态的垂直激发波长分别为179nm、120nm、111nm、110nm、100nm均位于紫外区内。
3.手动修改输入方式，其中NSTATE=5，MULT=3
甲酸分子（HCOOH）分子的5个三重态的垂直激发能
CI-SINGLESEXCITATIONENERGIES
STATEHARTREEEVKCAL/MOLCM-1
3A0.20001915305.4428125.513943899.13
3A0.20314047205.5277127.472644584.18
3A0.33589394099.1401210.776773720.20
3A0.377525179610.2730236.900782857.20
3A0.403189161810.9713253.005188489.79
因此，5个三重态的垂直激发波长分别为198nm、196nm、122nm、116nm、109nm均位于紫外区内。
4.第一个单重态的绝热激发能
对第1、2个单重态优化
手动修改输入方式，其中NSTATE=2，MULT=1，ISTATE=2
---------------------------------------------------------------------
CI-SINGLESEXCITATIONENERGIES
STATEHARTREEEVKCAL/MOLCM-1
---------------------------------------------------------------------
1A0.15852992474.313899.479034793.30
1A0.25436281766.9216159.615155826.19
因此，第1、2个单重态的绝热激发波长为287nm、179nm，均位于紫外区内。
5.第1、2个三重态的绝热激发能
---------------------------------------------------------------------
CI-SINGLESEXCITATIONENERGIES
STATEHARTREEEVKCAL/MOLCM-1
---------------------------------------------------------------------
3A0.03265206130.888520.48957166.30
3A0.07563332242.058147.460616599.60
因此，第1、2个三重态的绝热激发波长为1395nm、602nm，均不在紫外区。
6．再用HF/6-31G（d）优化三重态的第一激发态
Energy=-118374.261193Kcal/Mol（-188.641549Hartrees）
11-4-3
GIAOCHEMICALSHIELDINGTENSOR（PPM）:
ISOTROPIC
XYZSHIELDING
（ANISOTROPY）
2C2X214.8747-5.2980-8.9038
Y-7.6026196.89733.1084
Z-8.43053.5739184.5627
198.7782
EIGENVALS:
219.3736194.8588182.1023
（30.8931）
3C3X124.9389-72.6046-3.6690
Y-84.001921.1085-8.1135
Z-2.5830-5.8543164.1301
103.3925
EIGENVALS:
-21.0597164.3429166.8943
（95.2526）
6H6X30.1729-2.0497-3.9563
Y-1.120825.55340.9715
Z-4.71621.351442.0427
32.5896
EIGENVALS:
29.079843.585025.1042
（16.4930）
7H7X40.27800.80365.7076
Y1.643825.86632.9178
Z5.58252.658130.2227
32.1223
EIGENVALS:
43.099128.914824.3530
（16.4652）
8H8X28.4819-0.5993-0.7753
Y-0.868028.52184.0667
Z0.65174.791935.9271
30.9769
EIGENVALS:
28.592626.371137.9671
（10.4853）
9H9X28.8361-1.14250.0651
Y-1.664635.1747-3.5704
Z-0.4315-4.400728.1282
30.7130
EIGENVALS:
28.825126.182737.1313
（9.6274）
10H10X28.34270.0927-0.7583
Y4.081029.0622-0.8933
Z-1.3869-0.454617.8060
25.0703
EIGENVALS:
27.974329.552717.6838
（6.7236）
GIAOCHEMICALSHIELDINGTENSOR（PPM）:
ISOTROPIC
XYZSHIELDING
（ANISOTROPY）
1SI1X634.60040.04070.0583
Y0.0538636.3822-0.1581
Z0.0319-0.1451636.1752
635.7193
EIGENVALS:
634.5977636.0977636.4623
（1.1146）
2C2X257.55101.936510.1886
Y1.9283263.7570-2.5047
Z10.0880-2.5349250.2164
257.1748
EIGENVALS:
242.6262264.7022264.1960
（11.2911）
3C3X256.5299-1.7252-10.4962
Y-1.6060264.0716-2.1505
Z-10.3048-2.0732250.9449
257.1822
EIGENVALS:
242.6317264.4730264.4417
（10.9363）
4C4X256.7998-10.33941.9496
Y-10.3963250.88162.4541
Z1.78342.5601263.8557
257.1790
EIGENVALS:
242.5993264.5861264.3518
（11.1106）
5H5X31.52310.80045.0485
Y0.509326.89702.5961
Z3.33692.617241.9871
33.4690
EIGENVALS:
30.121543.826826.4588
（15.5366）
6H6X34.1297-7.8431-2.8037
Y-8.539336.40791.2317
Z-1.8206-0.011429.8420
33.4599
EIGENVALS:
43.766126.431730.1819
（15.4593）
7H7X34.59676.4993-5.3279
Y7.483834.8826-2.9672
Z-4.6009-1.752830.9032
33.4609
EIGENVALS:
43.774426.432430.1758
（15.4703）
8H8X34.1648-6.44345.1104
Y-7.485135.6383-3.0442
Z4.4623-1.836230.5965
33.4665
EIGENVALS:
43.784026.435430.1802
（15.4762）
9H9X31.1432-1.0155-4.4875
Y-0.694827.04553.0502
Z-2.76882.993442.2014
33.4634
EIGENVALS:
30.115343.815926.4589
（15.5288）
10H10X35.20507.94302.5788
Y8.676335.49300.6894
Z1.5250-0.456729.6883
33.4621
EIGENVALS:
43.770626.427430.1883
（15.4628）
11H11X34.53602.5875-7.8985
Y1.577629.66700.3423
Z-8.6273-0.868036.1479
33.4503
EIGENVALS:
43.769826.435030.1461
（15.4793）
12H12X34.66545.23886.4680
Y4.533830.59711.6800
Z7.49582.886435.0922
33.4516
EIGENVALS:
43.764826.432630.1572
（15.4698）
13H13X31.2755-4.64680.8331
Y-2.955542.1597-2.8437
Z0.5234-2.829526.9402
33.4585
EIGENVALS:
30.144343.802426.4287
（15.5158）
14C14X257.508310.1075-1.6153
Y10.0996249.98002.2484
Z-1.66352.1563264.0943
257.1942
EIGENVALS:
242.6118264.5720264.3988
（11.0667）
15H15X34.2370-5.1933-6.5390
Y-4.480430.86951.8425
Z-7.51153.080335.2672
33.4579
EIGENVALS:
43.778626.436430.1586
（15.4811）
16H16X34.4594-2.96937.8343
Y-1.964929.8329-0.0632
Z8.5378-1.296736.0791
33.4571
EIGENVALS:
43.776126.439930.1554
（15.4784）
17H17X31.55995.0393-0.8225
Y3.333941.9846-2.5012
Z-0.5583-2.516726.8337
33.4594
EIGENVALS:
30.149843.799426.4289
（15.5101）
因此，相对于TMS内标，1H的化学位移分别为：
Δδ（NH2）=32.4-33.4=-1.0
Δδ（CH2）=30.8-33.4=-2.6
Δδ（COOH）=25.1-33.4=-8.3
13C的化学位移分别为：
C2：
Δδ=198.8-257.2=-58.4
C3：
Δδ=103.4-257.2=-153.8
心得体会：
1.在紫外可见光谱的模拟中，通过模拟实验，我了解到激发价层电子时，存在两种不同的激发状态：
垂直激发和绝热激发。
通常意义上的光谱对应于垂直激发。
我们利用GAMESS程序中最简单的单组态相互作用方法（CIS）计算电子激发态。
所谓组态与组态相互作用指的就是组态与组态的线性组合。
我们先利用HF优化基态，再在不改变基态构型的基础上计算激发态。
2.对于IR、RAMAN谱图的模拟，几何构型的优化和频率计算应该在同一理论水平上，同时对于不同方法要考虑其相应的scaling
升级会员 