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Effective Valence Shell Hamiltonian Calculations on Spin-Orbit Coupling of SiH, SiH+, and SiH2+
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  • Effective Valence Shell Hamiltonian Calculations on Spin-Orbit Coupling of SiH, SiH+, and SiH2+
저자명
Chang. Ye-Won,Sun. Ho-Sung
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2003년|24권 6호|pp.723-727 (5 pages)
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

Recently the ab initio effective valence shell Hamiltonian method $H^v$ has been extended to treat spin-orbit coupling in atoms or molecules. The quasidegenerate many-body perturbation theory based $H^v$ 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 $H^v$ method is applied to calculating the fine structure splittings of the valence states of SiH, $SiH^+$, and $SiH^{2+}$ 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.