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ABSTRACT

Green and Zare 1977

Green, S., and R.N. Zare, 1977: Ab initio calculation of the spin-rotation constant for 2Π diatomics: Test of the Van Vleck approximation. J. Molec. Spectrosc., 64, 217-222, doi:10.1016/0022-2852(77)90261-2.

Ab initio calculations are carried out to determine γΠ (true), the first-order contribution to the spin-rotation constant, γΠ, for the X2Π ground states of OH, HF+, and HCl+ and their deuterated analogs. These calculations demonstrate that the contribution of this term to the experimentally determined value of γΠ is γ previously conjectured. Furthermore, it is found in the cases under study that the Van Vleck approximation to γΠ (true) significantly overestimates its importance, and a more realistic approximation is presented.

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