1205hw
•Calculate the first 13 singlet excited states of Hydrogen atom by using the CIS theoretical method with appropriate basis sets ( need to include diffuse functions or other elements ) then compare with the experimental values.
| unit: eV | ||||||||||||||
| H CIS | 1st | 2nd | 3rd | 4th | 5th | 6th | 7th | 8th | 9th | 10th | 11th | 12th | 13th | MAE |
| aug-cc-pvqz | 10.2 | 10.9 | 10.9 | 10.9 | 15.9 | 21.3 | 21.3 | 21.3 | 21.3 | 21.3 | 23.5 | 23.5 | 23.5 | 6.6 |
| d-aug-cc-pvqz | 10.2 | 10.2 | 10.2 | 10.2 | 12.1 | 13.2 | 13.2 | 13.2 | 13.4 | 13.4 | 13.4 | 13.4 | 13.4 | 0.8 |
| d-aug-cc-pvqz(+sp) | 10.2 | 10.2 | 10.2 | 10.2 | 12.1 | 12.1 | 12.1 | 12.1 | 12.8 | 13.4 | 13.4 | 13.4 | 13.4 | 0.5 |
| d-aug-cc-pvqz(+spdf) | 10.2 | 10.2 | 10.2 | 10.2 | 12.1 | 12.1 | 12.1 | 12.1 | 12.2 | 12.2 | 12.2 | 12.2 | 12.2 | 0.04 |
| EXP | 10.2 | 12.1 |
增加越多diffuse functions越接近實驗值
•Calculate the first 5 singlet excited states of Helium by using the CIS、CIS(D) theoretical method with appropriate basis sets then compare with the experimental values.
| unit: eV | ||||||
| He CIS | 1st | 2nd | 3rd | 4th | 5th | MAE |
| aug-cc-pvtz | 21.6 | 26.1 | 26.1 | 26.1 | 38.4 | 7.2 |
| d-aug-cc-pvtz | 21.2 | 21.9 | 21.9 | 21.9 | 23.9 | 1.7 |
| aug-cc-pvqz | 21.4 | 24.7 | 24.7 | 24.7 | 34.9 | 5.6 |
| d-aug-cc-pvqz | 21.1 | 21.8 | 21.8 | 21.8 | 23.8 | 1.6 |
| d-aug-cc-pvqz(+spdf) | 21.1 | 21.7 | 21.7 | 21.7 | 23.4 | 1.5 |
| EXP | 19.8 | 20.6 |
| unit: eV | ||||||
| He CISD | 1st | 2nd | 3rd | 4th | 5th | MAE |
| aug-cc-pvtz | 21.1 | 25.6 | 25.6 | 25.6 | 38.0 | 6.7 |
| d-aug-cc-pvtz | 20.7 | 21.5 | 21.5 | 21.5 | 23.4 | 1.3 |
| aug-cc-pvqz | 21.1 | 24.3 | 24.3 | 24.3 | 34.5 | 5.3 |
| d-aug-cc-pvqz | 20.8 | 21.5 | 21.5 | 21.5 | 23.4 | 1.3 |
| d-aug-cc-pvqz(+spdf) | 20.8 | 21.4 | 21.4 | 21.4 | 23.0 | 1.2 |
| EXP | 19.8 | 20.6 |
增加越多diffuse functions越接近實驗值，使用CISD也比使用CIS更接近實驗值
experimental value : NIST Atomic Spectra Database