Spectroscopic effects of first-order relativistic vibronic coupling in linear triatomic molecules

Abstract

It has recently been shown that there exists, in addition to the well-known nonrelativistic Renner-Teller coupling, a linear (that is, of the first order in the bending distortion) vibronic-coupling mechanism of relativistic (that is, spin-orbit) origin in 2II electronic states of linear molecules [L. V. Poluyanov and W. Domcke, Chem. Phys. 301, 111 (2004)]. The generic aspects of the relativistic linear vibronic-coupling mechanism have been analyzed in the present work by numerical calculations of the vibronic spectrum for appropriate models. The vibronic and spin-orbit parameters have been determined by accurate ab initio electronic-structure calculations for the X 2II states of a series of triatomic radicals and radical cations. It is shown for the example of GeCH that the relativistic linear vibronic-coupling mechanism provides a quantitative explanation of the pronounced perturbations in the vibronic spectrum of the X 2II state of GeCH, which previously have been termed "Sears resonances" [S.-G. He, H. Li, T. C. Smith, D. J. Clouthier, and A. J. Merer, J. Chem. Phys. 119, 10115 (2003)]. The X 2II vibronic spectra of the series BS2, CS2+, OCS+, and OBS illustrate the interplay of nonrelativistic and relativistic vibronic-coupling mechanisms in Renner-Teller systems.