Stimulated Emission Pumping Spectroscopy of SiH2: First Observation of the Spin-Orbit Interaction between the X 1A1 and the a 3B1 States
H. Ishikawa, Y. Muramoto, and N. Mikami,
J. Mol. Spectrosc. 216, 90 (2002).

Stimulated emission pumping spectra of the A 1B1- X 1A_1 transition of SiH2 radical were observed in order to obtain information about the a 3B1 state through the spin-orbit interaction. The vibrational level structure of the X state, which is the basis of the present observation of the triplet state, was well described with a polyad structure, in which both the 1ν1:2ν2 Fermi and the 2ν1:2ν3 Darling-Dennison anharmonic resonances were considered. In the P=10 polyad, four sets of spin-orbit perturbations were observed for the first time. The triplet state observed at about 9640 cm-1 from the (000) level of the X state was tentatively assigned to be the a 3B1 (030) level. An analysis of the spin-orbit interaction showed that the interaction energies of the spin-orbit coupling are 0.73-3.13 cm-1. This value is rather smaller than that expected based on the comparison with CH2. This is considered to be due to poor overlap between the vibrational wave functions in the a and the X state.

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