| Autor: |
Wadt, W. R., Moomaw, W. R. |
| Zdroj: |
Molecular Physics; June 1973, Vol. 25 Issue: 6 p1291-1303, 13p |
| Abstrakt: |
A general framework is developed for the theoretical treatment of d-orbital contributions of heavy atoms to the spin-orbit coupling of planar molecules. Unlike pπ orbitals for which only three-centre spin-orbit terms are non-vanishing, it is shown that a number of one- and two-centre terms will contribute. The case of thiophene (C4H4S) is examined, and all one- and two-centre integrals are evaluated explicitly. Although the two-centre terms are individually only a few per cent of the one-centre term, it is found that because of the large number of two-centre terms, they usually dominate the one-centre term. In thiophene, it is found that the contribution of individual dπ terms is on the order of 0·02-2·0 cm-1, which is comparable in magnitude to other contributions. An examination of the results as a function of effective nuclear charge and internuclear distance is also made. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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