(b)
在目录下创建nwchem与tmp文件夹
修改run_job.sh如下:
#!/bin/bash
nohup /opt/nwchem/bin/LINUX64/nwchem Benzene.nw >& 1.out &
修改Benzene.nw文件中路径
permanent_dir /home/dft_user26/home_work3/problem_2/problem_2/nwchem
scratch_dir /home/dft_user26/home_work3/problem_2/problem_2/tmp
运行程序
bash run_job.sh
运行完成后,打开1.out文件查看结果
搜索关键词Root,可查看相应的激发态
得到如下结果:
单重态
----------------------------------------------------------------------------
Root 1 singlet a 0.195708784 a.u. 5.3255 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -0.00000 Z -0.00000
Transition Moments XX 0.00000 XY 0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ -0.00000 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 20 a --- Virt. 22 a -0.70653
Occ. 21 a --- Virt. 23 a 0.70653
----------------------------------------------------------------------------
Root 2 singlet a 0.201045907 a.u. 5.4707 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y 0.00000 Z 0.00000
Transition Moments XX 0.00000 XY 0.00000 XZ -0.00000
Transition Moments YY -0.00000 YZ 0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 16 a --- Virt. 36 a 0.06857
Occ. 17 a --- Virt. 32 a 0.05767
Occ. 18 a --- Virt. 31 a -0.05767
Occ. 19 a --- Virt. 25 a -0.13947
Occ. 20 a --- Virt. 23 a -0.68758
Occ. 21 a --- Virt. 22 a -0.68758
----------------------------------------------------------------------------
Root 3 singlet a 0.271514533 a.u. 7.3883 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y 2.27580 Z -0.00000
Transition Moments XX -0.00000 XY 0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ 0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.93750
Occ. 12 a --- Virt. 29 a 0.05483
Occ. 14 a --- Virt. 34 a -0.06791
Occ. 15 a --- Virt. 33 a 0.06791
Occ. 16 a --- Virt. 28 a -0.09259
Occ. 16 a --- Virt. 34 a 0.07716
Occ. 17 a --- Virt. 31 a -0.10474
Occ. 17 a --- Virt. 35 a -0.07663
Occ. 18 a --- Virt. 32 a 0.10474
Occ. 20 a --- Virt. 22 a 0.67952
Occ. 21 a --- Virt. 23 a 0.67952
----------------------------------------------------------------------------
Root 4 singlet a 0.271514535 a.u. 7.3883 eV
----------------------------------------------------------------------------
Transition Moments X -2.27580 Y 0.00000 Z 0.00000
Transition Moments XX -0.00000 XY 0.00000 XZ 0.00000
Transition Moments YY 0.00000 YZ 0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.93750
Occ. 12 a --- Virt. 28 a -0.05483
Occ. 14 a --- Virt. 33 a -0.06791
Occ. 15 a --- Virt. 34 a -0.06791
Occ. 16 a --- Virt. 29 a -0.09259
Occ. 16 a --- Virt. 33 a -0.07716
Occ. 17 a --- Virt. 32 a -0.10474
Occ. 18 a --- Virt. 31 a -0.10474
Occ. 18 a --- Virt. 35 a 0.07663
Occ. 20 a --- Virt. 23 a -0.67952
Occ. 21 a --- Virt. 22 a 0.67952
----------------------------------------------------------------------------
Root 5 singlet a 0.337087837 a.u. 9.1726 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -0.00000 Z 0.00000
Transition Moments XX -4.42936 XY -0.00001 XZ 0.00000
Transition Moments YY 4.42936 YZ 0.00000 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 13 a --- Virt. 34 a -0.05712
Occ. 15 a --- Virt. 35 a 0.06288
Occ. 16 a --- Virt. 32 a -0.13127
Occ. 17 a --- Virt. 33 a -0.05745
Occ. 17 a --- Virt. 36 a -0.07859
Occ. 18 a --- Virt. 34 a -0.05745
Occ. 19 a --- Virt. 22 a 0.88340
Occ. 21 a --- Virt. 25 a 0.39076
----------------------------------------------------------------------------
Root 6 singlet a 0.337087839 a.u. 9.1726 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -0.00000 Z 0.00000
Transition Moments XX 0.00001 XY -4.42936 XZ -0.00000
Transition Moments YY -0.00001 YZ -0.00000 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 13 a --- Virt. 33 a -0.05712
Occ. 14 a --- Virt. 35 a -0.06288
Occ. 16 a --- Virt. 31 a 0.13127
Occ. 17 a --- Virt. 34 a -0.05745
Occ. 18 a --- Virt. 33 a 0.05745
Occ. 18 a --- Virt. 36 a -0.07859
Occ. 19 a --- Virt. 23 a -0.88340
Occ. 20 a --- Virt. 25 a -0.39076
----------------------------------------------------------------------------
Root 7 singlet a 0.354630769 a.u. 9.6500 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -0.00000 Z 0.00000
Transition Moments XX -0.00000 XY -0.00000 XZ -0.66192
Transition Moments YY -0.00000 YZ -0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 12 a --- Virt. 22 a 0.06165
Occ. 14 a --- Virt. 23 a -0.12883
Occ. 15 a --- Virt. 22 a 0.12883
Occ. 16 a --- Virt. 23 a -0.27653
Occ. 18 a --- Virt. 25 a 0.18153
Occ. 19 a --- Virt. 26 a 0.21831
Occ. 20 a --- Virt. 29 a 0.15119
Occ. 21 a --- Virt. 24 a 0.86599
Occ. 21 a --- Virt. 28 a -0.15119
----------------------------------------------------------------------------
Root 8 singlet a 0.354630771 a.u. 9.6500 eV
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -0.00000 Z 0.00000
Transition Moments XX 0.00000 XY -0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ -0.66192 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 12 a --- Virt. 23 a 0.06165
Occ. 14 a --- Virt. 22 a -0.12883
Occ. 15 a --- Virt. 23 a -0.12883
Occ. 16 a --- Virt. 22 a 0.27653
Occ. 17 a --- Virt. 25 a 0.18153
Occ. 19 a --- Virt. 27 a 0.21831
Occ. 20 a --- Virt. 24 a 0.86599
Occ. 20 a --- Virt. 28 a 0.15119
Occ. 21 a --- Virt. 29 a 0.15119
三重态
----------------------------------------------------------------------------
Root 1 triplet a 0.074348521 a.u. 2.0231 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 19 a --- Virt. 25 a 0.28613
Occ. 20 a --- Virt. 23 a 0.67056
Occ. 20 a --- Virt. 47 a -0.06563
Occ. 21 a --- Virt. 22 a 0.67056
Occ. 21 a --- Virt. 48 a -0.06563
----------------------------------------------------------------------------
Root 2 triplet a 0.148608157 a.u. 4.0438 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 20 a --- Virt. 23 a 0.70449
Occ. 21 a --- Virt. 22 a -0.70449
----------------------------------------------------------------------------
Root 3 triplet a 0.148608157 a.u. 4.0438 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 20 a --- Virt. 22 a -0.70449
Occ. 21 a --- Virt. 23 a -0.70449
----------------------------------------------------------------------------
Root 4 triplet a 0.186462043 a.u. 5.0739 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 20 a --- Virt. 22 a -0.70689
Occ. 21 a --- Virt. 23 a 0.70689
----------------------------------------------------------------------------
Root 5 triplet a 0.219201583 a.u. 5.9648 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 19 a --- Virt. 22 a 0.78309
Occ. 19 a --- Virt. 48 a -0.06800
Occ. 21 a --- Virt. 25 a 0.60402
Occ. 21 a --- Virt. 49 a -0.06391
----------------------------------------------------------------------------
Root 6 triplet a 0.219201583 a.u. 5.9648 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 19 a --- Virt. 23 a 0.78309
Occ. 19 a --- Virt. 47 a -0.06800
Occ. 20 a --- Virt. 25 a 0.60402
Occ. 20 a --- Virt. 49 a -0.06391
----------------------------------------------------------------------------
Root 7 triplet a 0.337007403 a.u. 9.1704 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 8 a --- Virt. 22 a -0.06215
Occ. 9 a --- Virt. 23 a -0.06215
Occ. 10 a --- Virt. 25 a 0.08580
Occ. 12 a --- Virt. 23 a -0.06440
Occ. 14 a --- Virt. 22 a 0.28514
Occ. 15 a --- Virt. 23 a 0.28514
Occ. 16 a --- Virt. 22 a -0.63262
Occ. 16 a --- Virt. 48 a 0.06497
Occ. 17 a --- Virt. 25 a -0.41525
Occ. 17 a --- Virt. 49 a 0.05947
Occ. 19 a --- Virt. 27 a -0.08358
Occ. 19 a --- Virt. 32 a -0.10846
Occ. 20 a --- Virt. 24 a -0.24496
Occ. 20 a --- Virt. 28 a -0.25097
Occ. 20 a --- Virt. 34 a 0.10173
Occ. 21 a --- Virt. 29 a -0.25097
Occ. 21 a --- Virt. 33 a -0.10173
Occ. 21 a --- Virt. 36 a -0.05781
----------------------------------------------------------------------------
Root 8 triplet a 0.337007407 a.u. 9.1704 eV
----------------------------------------------------------------------------
Transition Moments Spin forbidden
Oscillator Strength Spin forbidden
Occ. 8 a --- Virt. 23 a -0.06215
Occ. 9 a --- Virt. 22 a 0.06215
Occ. 11 a --- Virt. 25 a 0.08580
Occ. 12 a --- Virt. 22 a -0.06440
Occ. 14 a --- Virt. 23 a 0.28514
Occ. 15 a --- Virt. 22 a -0.28514
Occ. 16 a --- Virt. 23 a 0.63262
Occ. 16 a --- Virt. 47 a -0.06497
Occ. 18 a --- Virt. 25 a -0.41525
Occ. 18 a --- Virt. 49 a 0.05947
Occ. 19 a --- Virt. 26 a -0.08358
Occ. 19 a --- Virt. 31 a 0.10846
Occ. 20 a --- Virt. 29 a -0.25097
Occ. 20 a --- Virt. 33 a -0.10173
Occ. 20 a --- Virt. 36 a 0.05781
Occ. 21 a --- Virt. 24 a -0.24496
Occ. 21 a --- Virt. 28 a 0.25097
Occ. 21 a --- Virt. 34 a -0.10173
所以对于第一问有:
得到了8个激发态,其激发能如下:
单重态:
- 5.3255 eV
- 5.4707 eV
- 7.3883 eV
- 7.3883 eV
- 9.1726 eV
- 9.1726 eV
- 9.6500 eV
- 9.6500 eV
三重态:
9. 2.0231 eV
10. 4.0438 eV
11. 4.0438 eV
12. 5.0739 eV
13. 5.9648 eV
14. 5.9648 eV
15. 9.1704 eV
16. 9.1704 eV
(c)
在对称性相同的激发态之间,电偶极矩不会发生变化,因此它们之间的跃迁不会导致偶极跃迁。
在本题中,单重态的 1、2、5、6、7、8 号激发态的激发能与基态有较大的能量差异,因此它们的跃迁对应的波长可能在紫外光区域。而三重态的 2、4、5、6、7、8 号激发态的激发能与基态有较小的能量差异,因此它们的跃迁对应的波长可能在可见光区域。
因为只有在电偶极矩发生变化的激发态之间才会发生光激发导致的电偶极跃迁,因此在单重态中只有第 3 和第 4 号激发态及在三重态中只有第 2 号激发态满足电偶极跃迁选择定则。这是因为这些激发态的电偶极矩与基态不同,可能发生光激发导致的偶极跃迁。