The spectrum of singlet SiH2

Abstract

We report a theoretical study of the two lowest singlet electronic states ([Formula: see text]1A1 and Ã1B1) of silylene SiH2. These states become degenerate as a 1Δg state at linear configurations and are subject to the Renner effect. In ab initio calculations we have determined the potential energy and dipole moment surfaces for each state, and the transition moment surface between the states. Parameterized analytical functions have been fitted through the various sets of ab initio points, and the parameter values obtained for the potential energy surfaces have been further refined in fittings to experimental spectroscopic data. In these latter fittings, we use as input data experimentally derived energy differences together with ab initio points. In this manner, we achieve refined potential energy surfaces that behave reasonably also in regions of configuration space that are not sampled by the wavefunctions of the states for which experimentally derived energies are available. The calculation of rovibronic energies, the fittings to experimentally derived energies, and simulations of Ã1B1 → [Formula: see text]1A1 emission spectra of SiH2 have been carried out with the RENNER program system. The higher excited vibrational states of [Formula: see text]1A1 SiH2 form polyads of heavily interacting states and many polyad states have been observed in dispersed fluorescence studies. The present theoretical work shows that owing to the heavy interaction between the states in the polyads, it is difficult to obtain unambiguous assignments for them.Key words: silylene, RENNER, ab initio.PACS Nos.: 31.15.Ar, 33.20.Wr, 33.20.Ea