武汉大学分子模拟实验作业第十一章光谱模拟.docx

1、武汉大学分子模拟实验作业第十一章光谱模拟11-4-1PM3HF/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)）- GAMESS Interface -Model: Untitled-1GAMESS Job: Minimize (Energy/Geometry) RHF/6-31G(d)Finish energy = -25222.830226 Kcal/Mol (-40.195172 Hartrees)-PUNCH中Hessian数据$HESSENERGY IS -40.1951717590 E(NUC) IS

2、 13.5110377539 1 1 6.21632110E-01 1.74972133E-06-1.29287921E-06-5.76377714E-02-2.38972813E-03 1 2-1.47162917E-03-5.76204512E-02-1.30816035E-03 1.05566661E-03-2.52268416E-01 1 3 1.06162551E-02 1.38219883E-01-2.54104975E-01-6.92012964E-03-1.37802624E-01 2 1 1.74972133E-06 6.21813073E-01-6.80057005E-06

3、-2.38974905E-03-2.70385412E-01 2 2-1.31031330E-01-1.30813608E-03-2.35352893E-01 1.43430231E-01 1.06164001E-02 2 3-5.82046816E-02-7.53867767E-03-6.92025131E-03-5.78695874E-02-4.85335621E-03 3 1-1.29287921E-06-6.80057005E-06 6.21714867E-01-1.47162756E-03-1.31030042E-01 3 2-1.38307089E-01 1.05563707E-0

4、3 1.43428877E-01-1.73357682E-01 1.38221844E-01 3 3-7.53868172E-03-1.55776362E-01-1.37804561E-01-4.85333910E-03-1.54273139E-01 4 1-5.76377714E-02-2.38974905E-03-1.47162756E-03 5.41600392E-02 2.65410072E-03 4 2 1.63446608E-03-1.19851512E-03-1.47447954E-04-1.07029186E-04 2.65783682E-03 4 3 2.85870569E-

5、02 1.52166565E-02 2.01830720E-03-2.87039647E-02-1.52724699E-02 5 1-2.38972813E-03-2.70385412E-01-1.31030042E-01 2.65410072E-03 2.90441750E-01 5 2 1.45528290E-01-2.49548353E-04-2.26823271E-02-1.62531622E-02 9.74616987E-04 5 3 1.02976927E-03 7.28948034E-04-9.89454108E-04 1.59604004E-03 1.02564638E-03

6、6 1-1.47162917E-03-1.31031330E-01-1.38307089E-01 1.63446608E-03 1.45528290E-01 6 2 1.43752523E-01 2.51428487E-04 2.12611128E-02 1.65411509E-02-1.99823320E-03 6 3-1.79400752E-02-1.10299914E-02 1.58396169E-03-1.78183387E-02-1.09567585E-02 7 1-5.76204512E-02-1.30813608E-03 1.05563707E-03-1.19851512E-03

7、-2.49548353E-04 7 2 2.51428487E-04 5.41408205E-02 1.45283744E-03-1.17240537E-03 2.12099157E-03 7 3-2.64321242E-02 1.86833027E-02 2.55705097E-03 2.65369708E-02-1.88179612E-02 8 1-1.30816035E-03-2.35352893E-01 1.43428877E-01-1.47447954E-04-2.26823271E-02 8 2 2.12611128E-02 1.45283744E-03 2.51533076E-0

8、1-1.59298584E-01-1.20048372E-03 8 3 3.51560419E-03-2.87146434E-03 1.20324961E-03 2.98642641E-03-2.51964271E-03 9 1 1.05566661E-03 1.43430231E-01-1.73357682E-01-1.07029186E-04-1.62531622E-02 9 2 1.65411509E-02-1.17240537E-03-1.59298584E-01 1.82681165E-01-1.53861599E-03 9 3 1.61487816E-02-1.29789241E-

9、02 1.76238632E-03 1.59730755E-02-1.28858710E-0210 1-2.52268416E-01 1.06164001E-02 1.38221844E-01 2.65783682E-03 9.74616987E-0410 2-1.99823320E-03 2.12099157E-03-1.20048372E-03-1.53861599E-03 2.70331804E-0110 3-1.17914498E-02-1.53520349E-01-2.28423634E-02 1.40094028E-03 1.88356223E-0211 1 1.06162551E

10、-02-5.82046816E-02-7.53868172E-03 2.85870569E-02 1.02976927E-0311 2-1.79400752E-02-2.64321242E-02 3.51560419E-03 1.61487816E-02-1.17914498E-0211 3 5.47857482E-02 8.37323133E-03-9.79713937E-04-1.12654252E-03 9.56718493E-0412 1 1.38219883E-01-7.53867767E-03-1.55776362E-01 1.52166565E-02 7.28948034E-04

11、12 2-1.10299914E-02 1.86833027E-02-2.87146434E-03-1.29789241E-02-1.53520349E-0112 3 8.37323133E-03 1.63158934E-01-1.85991465E-02 1.30795071E-03 1.66262094E-0213 1-2.54104975E-01-6.92025131E-03-1.37804561E-01 2.01830720E-03-9.89454108E-0413 2 1.58396169E-03 2.55705097E-03 1.20324961E-03 1.76238632E-0

12、3-2.28423634E-0213 3-9.79713937E-04-1.85991465E-02 2.72371836E-01 7.68616361E-03 1.53057090E-0114 1-6.92012964E-03-5.78695874E-02-4.85333910E-03-2.87039647E-02 1.59604004E-0314 2-1.78183387E-02 2.65369708E-02 2.98642641E-03 1.59730755E-02 1.40094028E-0314 3-1.12654252E-03 1.30795071E-03 7.68616361E-

13、03 5.44135606E-02 5.39063125E-0315 1-1.37802624E-01-4.85335621E-03-1.54273139E-01-1.52724699E-02 1.02564638E-0315 2-1.09567585E-02-1.88179612E-02-2.51964271E-03-1.28858710E-02 1.88356223E-0215 3 9.56718493E-04 1.66262094E-02 1.53057090E-01 5.39063125E-03 1.61489425E-01 $END11-4-21. 利用GAMESS程序HF/6-31

14、G（d）理论水平优化基态 Total Energy = -118450.03822 Kcal/Mol2. 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-SINGLES EXCITATION ENERGIES STATE HARTREE EV KCAL/MOL CM-1 1A 0.2286267696 6.2213 143.4655 50177.78 1A 0.3600863064 9.7984 225.9576 79029.81 1A 0.3720432316 10.1238 233.4607 81654.05 1A 0.4036646121

15、 10.9843 253.3034 88594.14 1A 0.4494257606 12.2295 282.0190 98637.55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-SINGLES EXCITATION ENERGIES STATE HARTREE EV KCAL/MOL CM-1 3A 0.2000191530 5.4428 125.5139 43899.13 3A 0.2031404720 5.

16、5277 127.4726 44584.18 3A 0.3358939409 9.1401 210.7767 73720.20 3A 0.3775251796 10.2730 236.9007 82857.20 3A 0.4031891618 10.9713 253.0051 88489.79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-SINGLES EXCITATION ENERGIES STA

17、TE HARTREE EV KCAL/MOL CM-1 - 1A 0.1585299247 4.3138 99.4790 34793.30 1A 0.2543628176 6.9216 159.6151 55826.19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-SINGLES EXCITATION ENERGIES STATE HARTREE EV KCAL/MOL CM-1 - 3A 0.0326520613 0.8885 20.4895 7166.30 3A 0.0756333224 2.0581 47.460

18、6 16599.60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 = -118374.261193 Kcal/Mol (-188.641549 Hartrees)11-4-3GIAO CHEMICAL SHIELDING TENSOR (PPM): ISOTROPIC X Y Z SHIELDING ( ANISOTROPY ) 2 C2 X 214.8747 -5.2980 -8.9038 Y -7.6026 196.8973 3.1084 Z -8.4305 3.5739 184.5627 19

19、8.7782 EIGENVALS: 219.3736 194.8588 182.1023 ( 30.8931 ) 3 C3 X 124.9389 -72.6046 -3.6690 Y -84.0019 21.1085 -8.1135 Z -2.5830 -5.8543 164.1301 103.3925 EIGENVALS: -21.0597 164.3429 166.8943 ( 95.2526 ) 6 H6 X 30.1729 -2.0497 -3.9563 Y -1.1208 25.5534 0.9715 Z -4.7162 1.3514 42.0427 32.5896 EIGENVAL

20、S: 29.0798 43.5850 25.1042 ( 16.4930 ) 7 H7 X 40.2780 0.8036 5.7076 Y 1.6438 25.8663 2.9178 Z 5.5825 2.6581 30.2227 32.1223 EIGENVALS: 43.0991 28.9148 24.3530 ( 16.4652 ) 8 H8 X 28.4819 -0.5993 -0.7753 Y -0.8680 28.5218 4.0667 Z 0.6517 4.7919 35.9271 30.9769 EIGENVALS: 28.5926 26.3711 37.9671 ( 10.4

21、853 ) 9 H9 X 28.8361 -1.1425 0.0651 Y -1.6646 35.1747 -3.5704 Z -0.4315 -4.4007 28.1282 30.7130 EIGENVALS: 28.8251 26.1827 37.1313 ( 9.6274 ) 10 H10 X 28.3427 0.0927 -0.7583 Y 4.0810 29.0622 -0.8933 Z -1.3869 -0.4546 17.8060 25.0703 EIGENVALS: 27.9743 29.5527 17.6838 ( 6.7236 )GIAO CHEMICAL SHIELDIN

22、G TENSOR (PPM): ISOTROPIC X Y Z SHIELDING ( ANISOTROPY ) 1 SI1 X 634.6004 0.0407 0.0583 Y 0.0538 636.3822 -0.1581 Z 0.0319 -0.1451 636.1752 635.7193 EIGENVALS: 634.5977 636.0977 636.4623 ( 1.1146 ) 2 C2 X 257.5510 1.9365 10.1886 Y 1.9283 263.7570 -2.5047 Z 10.0880 -2.5349 250.2164 257.1748 EIGENVALS

23、: 242.6262 264.7022 264.1960 ( 11.2911 ) 3 C3 X 256.5299 -1.7252 -10.4962 Y -1.6060 264.0716 -2.1505 Z -10.3048 -2.0732 250.9449 257.1822 EIGENVALS: 242.6317 264.4730 264.4417 ( 10.9363 ) 4 C4 X 256.7998 -10.3394 1.9496 Y -10.3963 250.8816 2.4541 Z 1.7834 2.5601 263.8557 257.1790 EIGENVALS: 242.5993

24、 264.5861 264.3518 ( 11.1106 ) 5 H5 X 31.5231 0.8004 5.0485 Y 0.5093 26.8970 2.5961 Z 3.3369 2.6172 41.9871 33.4690 EIGENVALS: 30.1215 43.8268 26.4588 ( 15.5366 ) 6 H6 X 34.1297 -7.8431 -2.8037 Y -8.5393 36.4079 1.2317 Z -1.8206 -0.0114 29.8420 33.4599 EIGENVALS: 43.7661 26.4317 30.1819 ( 15.4593 )

25、7 H7 X 34.5967 6.4993 -5.3279 Y 7.4838 34.8826 -2.9672 Z -4.6009 -1.7528 30.9032 33.4609 EIGENVALS: 43.7744 26.4324 30.1758 ( 15.4703 ) 8 H8 X 34.1648 -6.4434 5.1104 Y -7.4851 35.6383 -3.0442 Z 4.4623 -1.8362 30.5965 33.4665 EIGENVALS: 43.7840 26.4354 30.1802 ( 15.4762 ) 9 H9 X 31.1432 -1.0155 -4.48

26、75 Y -0.6948 27.0455 3.0502 Z -2.7688 2.9934 42.2014 33.4634 EIGENVALS: 30.1153 43.8159 26.4589 ( 15.5288 ) 10 H10 X 35.2050 7.9430 2.5788 Y 8.6763 35.4930 0.6894 Z 1.5250 -0.4567 29.6883 33.4621 EIGENVALS: 43.7706 26.4274 30.1883 ( 15.4628 ) 11 H11 X 34.5360 2.5875 -7.8985 Y 1.5776 29.6670 0.3423 Z

27、 -8.6273 -0.8680 36.1479 33.4503 EIGENVALS: 43.7698 26.4350 30.1461 ( 15.4793 ) 12 H12 X 34.6654 5.2388 6.4680 Y 4.5338 30.5971 1.6800 Z 7.4958 2.8864 35.0922 33.4516 EIGENVALS: 43.7648 26.4326 30.1572 ( 15.4698 ) 13 H13 X 31.2755 -4.6468 0.8331 Y -2.9555 42.1597 -2.8437 Z 0.5234 -2.8295 26.9402 33.

28、4585 EIGENVALS: 30.1443 43.8024 26.4287 ( 15.5158 ) 14 C14 X 257.5083 10.1075 -1.6153 Y 10.0996 249.9800 2.2484 Z -1.6635 2.1563 264.0943 257.1942 EIGENVALS: 242.6118 264.5720 264.3988 ( 11.0667 ) 15 H15 X 34.2370 -5.1933 -6.5390 Y -4.4804 30.8695 1.8425 Z -7.5115 3.0803 35.2672 33.4579 EIGENVALS: 4

29、3.7786 26.4364 30.1586 ( 15.4811 ) 16 H16 X 34.4594 -2.9693 7.8343 Y -1.9649 29.8329 -0.0632 Z 8.5378 -1.2967 36.0791 33.4571 EIGENVALS: 43.7761 26.4399 30.1554 ( 15.4784 ) 17 H17 X 31.5599 5.0393 -0.8225 Y 3.3339 41.9846 -2.5012 Z -0.5583 -2.5167 26.8337 33.4594 EIGENVALS: 30.1498 43.7994 26.4289 (

30、 15.5101 )因此，相对于TMS内标，1H的化学位移分别为： (NH2)=32.4-33.4=-1.0 (CH2)=30.8-33.4=-2.6 (COOH)=25.1-33.4=-8.313C的化学位移分别为：C2：=198.8-257.2=-58.4C3：=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