1004HW
20221004
- Use Spartan or WebMO to calculate the electron affinity of atoms with atomic number 1~10, by using CCSD(T)、B3LYP and MP2 theories with 6-31G(d,p)、6-31++G(d,p) 、6-311G(2df,2p) and aug-cc-pVTZ basis sets, and do some simple statistical analysis. The unit of the electron affinity is kcal/mol .
- Organize the calculated data of electron affinity, and compare it with the experimental value, then present the result on your exercise page.
- Electron affinity (kcal/mol) 6-31G(d,p)
| MP2/6-31G(d,p) | B3LYP/6-31G(d,p) | CCSD(T)/6-31G(d,p) | exp. | |
| H | 39.4 | 24.1 | 37.6 | -17.4 |
| He | 860.6 | 829.9 | 862.8 | 5 |
| Li | 4.4 | -3.7 | -5.3 | -14.3 |
| Be | 45.3 | 34.3 | 47.1 | 4.3 |
| B | 33.2 | 25 | 35.8 | -5.5 |
| C | 5.4 | 1.3 | 9 | -29.1 |
| N | 54.2 | 35 | 54.2 | 1.4 |
| O | 14 | 5 | 16.4 | -33.7 |
| F | -24.7 | -24.2 | -19.9 | -77 |
| Ne | 1067.9 | 1009.1 | 1063.3 | 6.9 |
- Electron affinity (kcal/mol) 6-31++G(d,p)
| MP2/6-31++G(d,p) | B3LYP/6-31++G(d,p) | CCSD(T)/6-31++G(d,p) | exp. | |
| H | -3 | -20.5 | -16.8 | -17.4 |
| He | 127.9 | 117.4 | 68.1 | 5 |
| Li | -5.7 | -12 | -14.2 | -14.3 |
| Be | 15.3 | 5.3 | 8.5 | 4.3 |
| B | 1.2 | -9.6 | -5.3 | -5.5 |
| C | -22.7 | -31.4 | -28.1 | -29.1 |
| N | 20.1 | -3.2 | 6.9 | 1.7 |
| O | -25.1 | -37.4 | -30.7 | -33.7 |
| F | -78.5 | -81 | -76.4 | -77 |
| Ne | 172 | 157.6 | 140.6 | 6.9 |
- Electron affinity (kcal/mol) 6-311G(2df,2p)
| MP2/6-311G(2df,2p) | B3LYP/6-311G(2df,2p) | CCSD(T)/6-311G(2df,2p) | exp. | |
| H | 7.3 | -4.8 | -16.8 | -17.4 |
| He | 478.8 | -457.9 | 68.1 | 5 |
| Li | -4.7 | -9.8 | -14.2 | -14.3 |
| Be | 22.6 | 16.7 | 8.5 | 4.3 |
| B | 9.7 | 6.4 | -5.3 | -5.5 |
| C | -12.7 | -12.5 | -28.1 | -29.1 |
| N | 41.0 | 26.8 | 6.9 | 1.7 |
| O | 3.0 | -3.5 | -30.6 | -33.7 |
| F | -42.8 | -41.8 | -76.4 | -77 |
| Ne | 859.7 | 812.9 | 140.6 | 6.9 |
- Electron affinity (kcal/mol) aug-cc-pvtz
| MP2/aug-cc-pvtz | B3LYP/aug-cc-pvtz | CCSD(T)/aug-cc-pvtz | exp. | |
| H | -10.1 | -21 | -16.8 | -17.4 |
| He | 68.3 | 61.9 | 68.1 | 5 |
| Li | -8 | -12.8 | -14.2 | -14.3 |
| Be | 9.1 | 2.2 | 8.5 | 4.3 |
| B | -4.8 | -10.6 | -5.3 | -5.5 |
| C | -29.2 | -31.6 | -28.1 | -29.1 |
| N | 14.3 | -4.6 | 6.9 | 1.7 |
| O | -32.7 | -38.7 | -30.7 | -33.7 |
| F | -83.9 | -81.4 | -76.4 | -77 |
| Ne | 141.3 | 130.2 | 140.6 | 6.9 |
- Mean absolute error
| 6-31G(d,p) | 6-31++G(d,p) | 6-311G(2df,2p) | aug-cc-pvtz | |
| H | 81.1 | 6 | 6 | 3.8 |
| He | 846.1 | 99.5 | 99.5 | 61.1 |
| Li | 12.8 | 3.5 | 3.5 | 2.6 |
| Be | 37.9 | 5.4 | 5.4 | 3.7 |
| B | 36.8 | 3.7 | 3.7 | 2 |
| C | 34.3 | 3.2 | 3.2 | 1.2 |
| N | 46.1 | 9.5 | 9.5 | 8.2 |
| O | 45.5 | 5.1 | 5.1 | 3 |
| F | 54.1 | 2 | 2 | 4 |
| Ne | 1039.9 | 149.8 | 149.8 | 130.5 |
- Analysis
Conclusions
- 增加 diffuse function 可以降低誤差