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Renner-Teller, spin-orbit and Fermi-resonance interactions in X2Π NCS investigated by LIF spectroscopy

 

作者: F.J. Northrup,   TrevorJ. Sears,  

 

期刊: Molecular Physics  (Taylor Available online 1990)
卷期: Volume 71, issue 1  

页码: 45-64

 

ISSN:0026-8976

 

年代: 1990

 

DOI:10.1080/00268979000101631

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

The electronic spectrum of the NCS radical is obtained following UV excimer-laser photolysis of C2H5NCS in a large excess of inert gas in a supersonic free jet expansion. The spectrum is complicated by the presence of Renner-Teller and spin-orbit coupling and a Fermi resonance between the doubly excited bending vibration andv3, the CS stretching vibration. Bending vibronic level structure in the X2Π ground state of the radical is determined from a variety of laser-induced-fluorescence techniques, including stimulated-emission pumping. These energy levels are used to determine vibronic-coupling parameters for the radical. Coupling between close-lying bending levels with differentv2andK(= Λ +l) is found to be important because some of these levels are close together in NCS owing to the very large spin-orbit coupling. A parameter representing this effect is related to the dipolar contribution ε1to the Renner-Teller coupling parameter ε by applying perturbation theory to a simple model involving the X2Π and B2Σ+electronic states of NCS. This procedure results in an estimate for ε1that agrees approximately with that determined from the vibronic-coupling parametergK, assuming the same model for the interacting electronic states.

 

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