郭騰予 第四週作業
Use Gaussian、 Spartan or WebMO to calculate the Electron Affinity of atoms with atomic number 3~18, by using B3LYP、MP2 and M062X theoretical methods with 6-31G**、6-311G**、6-31+G** and 6-311+G** basis set, and do some simple statistical analysis.
Definition of Electron Affinity:
A(g) + e -→ A-(g) ΔE = EA or
A-(g) → A(g) + e - ΔE = EA
Table 1 6-31G** with different methods
| 單位:kcal/mol | MP2 | B3LYP | M062X | Experimental value |
| H | -39.4 | -24.1 | -29.8 | 17.4 |
| Li | -4.4 | 3.7 | 2.2 | 14.3 |
| Be | -62.1 | -34.3 | -40.6 | 0 |
| B | -33.2 | -25.0 | -28.8 | 5.5 |
| C | -5.4 | -1.3 | -1.0 | 29.1 |
| N | -54.2 | -35.0 | -39.9 | -1.7 |
| O | -14.0 | -5.0 | -5.3 | 33.7 |
| F | 24.7 | 24.2 | 25.7 | 77.0 |
| Na | 1.4 | 10.3 | 9.3 | 12.6 |
| Mg | -23.1 | -17.4 | -22.8 | 0 |
| Al | -5.0 | 0.8 | -2.0 | 10.5 |
| Si | -23.8 | -6.9 | -7.2 | 31.9 |
| P | -14.5 | 6.6 | 5.6 | 17.1 |
| S | 22.1 | 38.1 | 38.1 | 47.9 |
| Cl | 62.5 | 72.8 | 74.1 | 83.3 |
Figure 1
Table 2 6-311G**with different methods
| 單位:kcal/mol | MP2 | B3LYP | M062X | Experimental value |
| H | -10.6 | 4.8 | -0.1 | 17.4 |
| Li | 3.6 | 9.8 | 8.8 | 14.3 |
| Be | -25.7 | -17.0 | -23.0 | 0 |
| B | -13.3 | -6.4 | -9.2 | 5.5 |
| C | 8.6 | 12.7 | 13.5 | 29.1 |
| N | -48.7 | -27.5 | -32.8 | -1.7 |
| O | -9.7 | 3.6 | 2.5 | 33.7 |
| F | 37.1 | 42.4 | 42.5 | 77.0 |
| Na | 2.7 | 10.3 | 9.9 | 12.6 |
| Mg | -19.2 | -13.8 | -18.5 | 0 |
| Al | -1.1 | 5.3 | 2.9 | 10.5 |
| Si | -18.3 | -0.1 | -1.0 | 31.9 |
| P | -1.9 | 20.0 | 18.1 | 17.1 |
| S | 33.0 | 50.2 | 48.7 | 47.9 |
| Cl | 72.2 | 84.4 | 84.4 | 83.3 |
Figure 2
Table 3 6-31+G** with different methods
| 單位:kcal/mol | MP2 | B3LYP | M062X | Experimental value |
| H | -39.4 | -24.1 | -29.8 | 17.4 |
| Li | 5.7 | 12.6 | 11.4 | 14.3 |
| Be | -15.3 | -5.3 | -10.6 | 0 |
| B | -1.2 | 9.6 | 4.2 | 5.5 |
| C | 22.7 | 31.4 | 27.5 | 29.1 |
| N | -20.1 | 3.2 | -5.8 | -1.7 |
| O | 25.1 | 37.4 | 30.1 | 33.7 |
| F | 78.5 | 81.0 | 73.5 | 77.0 |
| Na | 5.9 | 13.7 | 13.0 | 12.6 |
| Mg | -11.2 | -5.4 | -9.6 | 0 |
| Al | 1.5 | 8.2 | 5.6 | 10.5 |
| Si | -9.9 | 7.3 | 5.6 | 31.9 |
| P | -0.9 | 20.9 | 18.3 | 17.1 |
| S | 33.3 | 50.6 | 48.6 | 47.9 |
| Cl | 73.5 | 85.6 | 84.6 | 83.3 |
Figure 3
Table 4 6-311+G** with different methods
| 單位:kcal/mol | MP2 | B3LYP | M062X | Experimental value |
| H | -10.6 | 4.8 | -0.1 | 17.4 |
| Li | 6.6 | 12.9 | 8.8 | 14.3 |
| Be | -14.2 | -5.8 | -23.1 | 0 |
| B | 0.4 | 9.3 | -9.6 | 5.5 |
| C | 24.3 | 31.4 | 12.9 | 29.1 |
| N | -20.5 | 3.1 | -33.7 | -1.7 |
| O | 23.1 | 37.1 | 0.4 | 33.7 |
| F | 74.7 | 80.4 | 39.5 | 77.0 |
| Na | 6.1 | 13.5 | 9.7 | 12.6 |
| Mg | -10.9 | -5.2 | -18.6 | 0 |
| Al | 2.2 | 8.9 | 2.7 | 10.5 |
| Si | -9.8 | 3.7 | -1.2 | 31.9 |
| P | -0.8 | 21.0 | 17.1 | 17.1 |
| S | 33.3 | 50.5 | 47.9 | 47.9 |
| Cl | 73.7 | 85.9 | 83.7 | 83.3 |
Figure 4
Figure 5
Mean unsigned error(MUE) unit:kcal/mole
MP2:30.4
B3LYP:20.6
M062X:22.6
Figure 6
Mean unsigned error(MUE) unit:kcal/mole
MP2:20.6
B3LYP:11.8
M062X:13.2
Figure 7
Mean unsigned error(MUE) unit:kcal/mole
MP2:13.0
B3LYP:6.1
M062X:6.6
Figure 8
Mean unsigned error(MUE) unit:kcal/mole
MP2:11.2
B3LYP:4.6
M062X:13.5
Use Gaussian、 Spartan or WebMO to calculate the Electron Affinity of atoms with Hydrogen and Helium, by using B3LYP、MP2 and M062X theoretical methods with 6-31G**、6-311G**、6-31++G** and 6-311++G** basis set, and do some simple statistical analysis.
Table 5 6-31++G** with different methods
| 單位:kcal/mol | MP2 | B3LYP | M062X | Experimental value |
| H | 3.0 | 20.5 | 13.4 | 17.4 |
| He | -127.9 | -117.4 | -114.5 | -5.0 |
Figure 8
Table 6 6-311++G** with different methods
| 單位:kcal/mol | MP2 | B3LYP | M062X | Experimental value |
| H | 3.6 | 20.0 | 13.3 | 17.4 |
| He | -116.6 | -106.0 | -104.4 | -5.0 |
Figure 9
Conclusion:The B3LYP is the best method to calculate the electron affinity.
Reference
Atkin, P.; de Paula, J., Atkins’ physical chemistry. WH Freeman and Company Books 2006