Higher order spin-orbit distortion of the isotropic hyperfine hamiltonian in high multiplicity Σ electronic states
Titel:
Higher order spin-orbit distortion of the isotropic hyperfine hamiltonian in high multiplicity Σ electronic states
Auteur:
Cheung, A.S-C. Merer, A. J.
Verschenen in:
Molecular physics
Paginering:
Jaargang 46 (1982) nr. 1 pagina's 111-128
Jaar:
1982-05
Inhoud:
The theory of the higher order cross terms between the spin-orbit operator and the isotropic hyperfine operator in Σ electronic states of quarter and higher multiplicity has been examined. It is found that for S ≥ 3/2 spin-orbit distortion of the Fermi contact interaction gives rise to another independently-determinable parameter, which is permitted by group theory. This parameter is needed to account for the hyperfine structure of the C4Σ- state of VO, where there are nearby electronic states interacting strongly through the spin-orbit operator. There is a close similarity between the new effect and the second spin-rotation constant required for 4Σ states which has been discussed by Hougen (1962, Can. J. Phys., 40, 598) and Brown and Milton (1976, Molec. Phys., 31, 409). The new effect is not in fact restricted to Σ states, but is general for all values of Λ (or K in non-linear polyatomic molecules).
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