Effective Valence Shell Hamiltonian Calculations on Spin-Orbit Coupling of SiH, SiH+, and SiH2+

Bulletin of the Korean chemical society

Hosung Sun¹  Ye Won Chang¹ 

关键词: Effective Hamiltonian;    Spin-orbit coupling;    SiH;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

Recently the ab initio effective valence shell Hamiltonian method Hv has been extended to treat spin-orbit coupling in atoms or molecules. The quasidegenerate many-body perturbation theory based Hv method has an advantage of determining the spin-orbit coupling energies of all valence states for both the neutral species and its ions with a similar accuracy from a single computation of the effective spin-orbit coupling operator. The new spin-orbit Hv method is applied to calculating the fine structure splittings of the valence states of SiH, SiH+, and SiH2+ not only to assess the accuracy of the method but also to investigate the spin-orbit interaction of highly excited states of SiH species. The computed spin-orbit splittings for ground states are in good agreement with experiment and the few available ab initio computations. The ordering of fine structure levels of the bound and quasi-bound spin-orbit coupled valence states of SiH and its ions, for which neither experiment nor theory is available, is predicted.

【 授权许可】

Unknown