Sub-Doppler spectroscopy of thioformaldehyde: Excited state perturbations and evidence for rotation-induced vibrational mixing in the ground state

Article abstract of DOI:10.1063/1.468287

High-resolution intracativity dye laser spectroscopy has been used to obtain sub-Doppler spectra of transitions to 350 rotational levels in the 4₀¹ band of the <*> ¹A₂-<*> ¹A₁ electronic transition of thioformaldehyde.Ground state combination differences from the sub-Doppler spectra, combined with microwave and infrared data, have been used to improve the ground state rotational and centrifugal distortion constants of H2CS.The upper state shows a remarkable number of perturbations.The largest of these are caused by nearby triplet levels, with matrix elements of 0.05-0.15 cm^-1.A particularly clear singlet-triplet avoided crossing in K_a' = 7 has been shown to be caused by interaction with the F₁ component of the 3¹6² vibrational level of the <*> ³A₂ state.At least 53percent of the S₁ levels show evidence of very small perturbations by high rovibronic levels of the ground state.The number of such perturbations is small at low J, but increases rapidly beyond J=5 such that 40percent-80percent of the observed S₁ levels of any given J are perturbed by ground state levels.Model calculations show that the density and J dependence of the number of perturbed levels can be explained if three is extensive rotation-induced mixing of the vibrational levels in the ground state.

Full text of DOI:10.1063/1.468287

SubDoppler spectroscopy of thioformaldehyde: Excited state perturbations and
evidence for rotationinduced vibrational mixing in the ground state
Dennis J. Clouthier, G. Huang, A. G. Adam, and A. J. Merer
Citation: The Journal of Chemical Physics 101, 7300 (1994); doi: 10.1063/1.468287
View online: http://dx.doi.org/10.1063/1.468287
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/101/9?ver=pdfcov
Published by the AIP Publishing
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