Electronic Spin Splitting Corrections
(subtract from ab initio heat of formation)
Correction energies
| |
|
correction |
| species | name |
cm-1 |
hartree |
kJ mol-1 |
| B |
Boron atom |
10.2 |
0.000046 |
0.122 |
| C |
Carbon atom |
29.6 |
0.000135 |
0.354 |
| C+ |
Carbon atom cation |
42.3 |
0.000193 |
0.506 |
| N+ |
Nitrogen atom cation |
88.9 |
0.000405 |
1.063 |
| O |
Oxygen atom |
78.0 |
0.000355 |
0.933 |
| F |
Fluorine atom |
134.7 |
0.000614 |
1.611 |
| F+ |
Fluorine atom cation |
168.1 |
0.000766 |
2.011 |
| Ne+ |
Neon atom cation |
260.1 |
0.001185 |
3.112 |
| Al |
Aluminum atom |
74.7 |
0.000340 |
0.894 |
| Si |
Silicon atom |
149.8 |
0.000682 |
1.792 |
| Si+ |
Silicon atom cation |
191.5 |
0.000873 |
2.291 |
| P+ |
Phosphorus atom cation |
315.6 |
0.001438 |
3.775 |
| S |
Sulfur atom |
196.0 |
0.000893 |
2.345 |
| Cl |
Chlorine atom |
293.7 |
0.001338 |
3.513 |
| Cl+ |
Chlorine atom cation |
343.0 |
0.001563 |
4.103 |
| Ar+ |
Argon atom cation |
477.2 |
0.002174 |
5.709 |
| Ti |
Titanium atom |
222.5 |
0.001014 |
2.662 |
| Ge |
Germanium atom |
969.0 |
0.004415 |
11.592 |
| Se |
Selenium atom |
944.8 |
0.004305 |
11.302 |
| Br |
Bromine atom |
1228.4 |
0.005597 |
14.695 |
| Br+ |
Bromine atom cation |
1471.9 |
0.006706 |
17.607 |
| I |
Iodine atom |
2534.4 |
0.011548 |
30.318 |
| CH |
Methylidyne |
14.0 |
0.000064 |
0.167 |
| OH |
Hydroxyl radical |
69.6 |
0.000317 |
0.833 |
| DO |
Hydroxyl-d |
69.6 |
0.000317 |
0.833 |
| LiO |
lithium oxide |
56.0 |
0.000255 |
0.670 |
| NO |
Nitric oxide |
59.9 |
0.000273 |
0.717 |
| CF |
Fluoromethylidyne |
38.6 |
0.000176 |
0.461 |
| FO |
Oxygen monofluoride |
98.1 |
0.000447 |
1.173 |
| NaO |
sodium monoxide |
53.6 |
0.000244 |
0.641 |
| SiH |
Silylidyne |
71.4 |
0.000325 |
0.854 |
| SiF |
silicon monofluoride |
80.9 |
0.000369 |
0.968 |
| PO |
Phosphorus monoxide |
112.0 |
0.000510 |
1.340 |
| DS |
Mercapto-d |
188.4 |
0.000858 |
2.253 |
| SH |
Mercapto radical |
188.5 |
0.000859 |
2.255 |
| NS |
Mononitrogen monosulfide |
110.8 |
0.000505 |
1.325 |
| SF |
Monosulfur monofluoride |
200.5 |
0.000914 |
2.399 |
| PS |
phosphorus sulfide |
160.4 |
0.000731 |
1.919 |
| CCl |
carbon monochloride |
67.5 |
0.000307 |
0.807 |
| ClO |
Monochlorine monoxide |
159.0 |
0.000724 |
1.902 |
| SiCl |
Clorosilylidyne |
103.3 |
0.000471 |
1.236 |
| SCl |
sulfur monochloride |
200.0 |
0.000911 |
2.393 |
| CuO |
Copper Monoxide |
139.5 |
0.000636 |
1.669 |
| BrO |
Bromine monoxide |
408.0 |
0.001859 |
4.881 |
| BO2 |
Boron dioxide |
75.1 |
0.000342 |
0.898 |
These corrections are obtained from the atomic energy levels (MOORE)
and the spin-orbit splittings from Herzberg.
They are a weighted average of the splittings of the lowest energy state.
For example Carbon atom has a 3P ground state with the following splittings:
| J |
Energy (cm-1) |
degeneracy | Energy * degeneracy |
| 0 | 0.0 | 1 | 0.0 |
| 1 | 16.4 | 3 | 49.2 |
| 2 | 43.5 | 5 | 217.5 |
|
| Total | 9 | 266.7 |
The degeneracy of each J level is 2*J+1. The weighted average is then 266.7 / 9 = 29.63 cm-1
References
Huber, K.P.; Herzberg, G., Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules,, Van Nostrand Reinhold Co., 1979
Moore, C.E.,Atomic Energy Levels,NBS467, 1949.
