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摘要
The 18 Lambda-S states correlated to the lowest dissociation (Si(P-3(g))+S(P-3(g))) limit are computed with high-level multireference configuration interaction (MRCI(SD)) approach through utilizing all-electron aug-cc-pwCVQZ-DK basis set. The scalar relativistic effect and the core-valence correlation effect of Si (2s(2)2p(6)) and S (2s(2)2p(6)) are taken into account. On the basis of calculated potential energy curves, the spectroscopic constants of the bound states are fitted, including equilibrium distance R-c, adiabatic transition energies T-c, harmonic vibrational frequencies w(c), anharmonic terms w(c)x(c), and rotational constant B-e. The electronic configurations at different bond lengths are given. The electronic dipole moments of 18 Lambda-S states are calculated, illuminating the influence of electronic configuration variation on electronic dipole moment. With the help of nonvanishing spin-orbit matrix elements including b(3)Pi and A(1)Pi as a function of the internuclear distance, the nearby state perturbations to b(3) Pi and A(1)Pi are discussed in detail. Finally, the transition dipole moments and Franck-Condon factors of A(1)Pi-X-1 Sigma(+) and E-1 Sigma(+)-X-1 Sigma(+) transitions are obtained, and radiative lifetimes of five lowest vibrational levels of the two singlet excited states are evaluated.
