1031作業
Calculate the structures and atomization energies (AE) of XHn (X = H~Ne) by using B3LYP、MP2 theoretical methods with 6-31+G(d,p)、aug-cc-pVTZ then compare with the experimental values.
1. structures
| bond length(Å) | |||||
| B3LYP/6-31+G(d,p) | B3LYP/aug-cc-pVTZ | MP2/6-31+G(d,p) | MP2/aug-cc-pVTZ | Exp | |
| H2 | 0.743 | 0.743 | 0.734 | 0.737 | 0.741 |
| LiH | 1.614 | 1.590 | 1.623 | 1.605 | 1.595 |
| BeH2 | 1.331 | 1.325 | 1.328 | 1.330 | 1.326 |
| BH3 | 1.193 | 1.188 | 1.186 | 1.187 | 1.190 |
| CH4 | 1.093 | 1.088 | 1.087 | 1.086 | 1.087 |
| NH3 | 1.016 | 1.013 | 1.012 | 1.012 | 1.012 |
| H2O | 0.965 | 0.962 | 0.963 | 0.961 | 0.958 |
| HF | 0.928 | 0.924 | 0.927 | 0.922 | 0.917 |
| bond length(Å) | |||||
| absolute error | B3LYP/6-31+G(d,p) | B3LYP/aug-cc-pVTZ | MP2/6-31+G(d,p) | MP2/aug-cc-pVTZ | |
| H2 | 0.002 | 0.002 | 0.007 | 0.004 | |
| LiH | 0.019 | 0.005 | 0.028 | 0.010 | |
| BeH2 | 0.005 | 0.001 | 0.002 | 0.004 | |
| BH3 | 0.003 | 0.002 | 0.004 | 0.003 | |
| CH4 | 0.006 | 0.001 | 0.000 | 0.001 | |
| NH3 | 0.004 | 0.001 | 0.000 | 0.000 | |
| H2O | 0.007 | 0.004 | 0.005 | 0.003 | |
| HF | 0.011 | 0.007 | 0.010 | 0.005 | |
| mean absolute error | 0.007 | 0.003 | 0.007 | 0.004 | |
| bond angle(degree) | |||||
| B3LYP/6-31+G(d,p) | B3LYP/aug-cc-pVTZ | MP2/6-31+G(d,p) | MP2/aug-cc-pVTZ | Exp | |
| H2 | - | - | - | - | - |
| LiH | - | - | - | - | - |
| BeH2 | 180.00 | 180.00 | 180.00 | 180.00 | 180.00 |
| BH3 | 120.00 | 120.00 | 120.00 | 120.00 | 120.00 |
| CH4 | 109.47 | 109.47 | 109.47 | 109.47 | 109.47 |
| NH3 | 108.07 | 107.23 | 108.06 | 106.77 | 106.67 |
| H2O | 105.75 | 105.09 | 105.42 | 104.12 | 104.48 |
| HF | - | - | - | - | - |
2. atomization energies (AE)
| B3LYP/6-31+G(d,p) | ||||||||
| XHn(Hartree) | X(Hartree) | H(Hartree) | n | AE(Hartree) | AE(kcal/mol) | Exp(kcal/mol) | absolute error(kcal/mol) | |
| H2 | -1.16949 | -0.50027 | -0.50027 | 1 | 0.16894 | 106.0 | 104.2 | 1.8 |
| LiH | -8.08207 | -7.49120 | -0.50027 | 1 | 0.09059 | 56.8 | 56.6 | 0.2 |
| BeH2 | -15.91138 | -14.67075 | -0.50027 | 2 | 0.24009 | 150.7 | 151.6 | 0.9 |
| BH3 | -26.60910 | -24.65956 | -0.50027 | 3 | 0.44871 | 281.6 | 270.3 | 11.3 |
| CH4 | -40.52612 | -37.85133 | -0.50027 | 4 | 0.67369 | 422.7 | 397.5 | 25.2 |
| NH3 | -56.56009 | -54.58777 | -0.50027 | 3 | 0.47150 | 295.9 | 280.3 | 15.6 |
| H2O | -76.42194 | -75.06760 | -0.50027 | 2 | 0.35379 | 222.0 | 221.6 | 0.4 |
| HF | -100.44098 | -99.73060 | -0.50027 | 1 | 0.21012 | 131.8 | 136.4 | 4.6 |
| mean absolute error | 7.5 | |||||||
| B3LYP/aug-cc-pVTZ | ||||||||
| XHn(Hartree) | X(Hartree) | H(Hartree) | n | AE(Hartree) | AE(kcal/mol) | Exp(kcal/mol) | absolute error(kcal/mol) | |
| H2 | -1.17115 | -0.50226 | -0.50226 | 1 | 0.16663 | 104.6 | 104.2 | 0.4 |
| LiH | -8.08736 | -7.49205 | -0.50226 | 1 | 0.09305 | 58.4 | 56.6 | 1.8 |
| BeH2 | -15.91715 | -14.67245 | -0.50226 | 2 | 0.24018 | 150.7 | 151.6 | 0.9 |
| BH3 | -26.61741 | -24.66389 | -0.50226 | 3 | 0.44674 | 280.3 | 270.3 | 10.0 |
| CH4 | -40.53842 | -37.85906 | -0.50226 | 4 | 0.67032 | 420.6 | 397.5 | 23.1 |
| NH3 | -56.58097 | -54.50241 | -0.50226 | 3 | 0.57178 | 358.8 | 280.3 | 78.5 |
| H2O | -76.45309 | -75.09418 | -0.50226 | 2 | 0.35440 | 222.4 | 221.6 | 0.8 |
| HF | -100.47902 | -99.76614 | -0.50226 | 1 | 0.21062 | 132.2 | 136.4 | 4.2 |
| mean absolute error | 15.0 | |||||||
| MP2/6-31+G(d,p) | ||||||||
| XHn(Hartree) | X(Hartree) | H(Hartree) | n | AE(Hartree) | AE(kcal/mol) | Exp(kcal/mol) | absolute error(kcal/mol) | |
| H2 | -1.14979 | -0.49823 | -0.49823 | 1 | 0.15333 | 96.2 | 104.2 | 8.0 |
| LiH | -8.00111 | -7.43156 | -0.49823 | 1 | 0.07132 | 44.8 | 56.6 | 11.8 |
| BeH2 | -15.80863 | -14.59558 | -0.49823 | 2 | 0.21658 | 135.9 | 151.6 | 15.7 |
| BH3 | -26.48031 | -24.56311 | -0.49823 | 3 | 0.42251 | 265.1 | 270.3 | 5.2 |
| CH4 | -40.36592 | -37.73661 | -0.49823 | 4 | 0.63637 | 399.3 | 397.5 | 1.8 |
| NH3 | -56.38385 | -54.45920 | -0.49823 | 3 | 0.42995 | 269.8 | 280.3 | 10.5 |
| H2O | -76.22006 | -74.88529 | -0.49823 | 2 | 0.33830 | 212.3 | 221.6 | 9.3 |
| HF | -100.20497 | -99.49882 | -0.49823 | 1 | 0.20792 | 130.5 | 136.4 | 5.9 |
| mean absolute error | 8.5 | |||||||
| MP2/aug-cc-pVTZ | ||||||||
| XHn(Hartree) | X(Hartree) | H(Hartree) | n | AE(Hartree) | AE(kcal/mol) | Exp(kcal/mol) | absolute error(kcal/mol) | |
| H2 | -1.15681 | -0.49982 | -0.49982 | 1 | 0.15716 | 98.6 | 104.2 | 5.6 |
| LiH | -8.01463 | -7.43271 | -0.49982 | 1 | 0.08211 | 51.5 | 56.6 | 5.1 |
| BeH2 | -15.82542 | -14.60119 | -0.49982 | 2 | 0.22460 | 140.9 | 151.6 | 10.7 |
| BH3 | -26.50802 | -24.57658 | -0.49982 | 3 | 0.43198 | 271.1 | 270.3 | 0.8 |
| CH4 | -40.41442 | -37.75956 | -0.49982 | 4 | 0.65558 | 411.4 | 397.5 | 13.9 |
| NH3 | -56.45198 | -54.49865 | -0.49982 | 3 | 0.45387 | 284.8 | 280.3 | 4.5 |
| H2O | -76.31520 | -74.95929 | -0.49982 | 2 | 0.35626 | 223.6 | 221.6 | 2.0 |
| HF | -100.32916 | -99.61211 | -0.49982 | 1 | 0.21724 | 136.3 | 136.4 | 0.1 |
| mean absolute error | 5.3 | |||||||
(unit:kcal/mol)
(unit:kcal/mol)
(unit:kcal/mol)
experimental value: Computational Chemistry Comparison and Benchmark DataBase