Calculation of the vibronic structure of the photodetachment spectra of CCCl- and CCBr-.
The vibronic structure of the closely spaced and strongly coupled X 2Sigma+ and A 2Pi states in the photodetachment spectra of CCCl- and CCBr- has been calculated by considering Sigma-Pi vibronic coupling together with spin-orbit coupling. The stretching modes are treated within the so-called linear-vibronic-coupling model. The vibronic and spin-orbit parameters have been determined by accurate ab initio electronic-structure calculations. While the nonrelativistic vibronic-coupling parameters are of approximately equal strength in CCCl and CCBr, the vibronic-coupling parameters of spin-orbit origin are found to be larger in the latter. The calculated photodetachment spectra of both systems are shown to exhibit a complicated vibronic structure due to strong Sigma-Pi vibronic coupling. The spectral envelopes of the calculated photodetachment spectra exhibit a double-hump reminiscent of strongly coupled Exe Jahn-Teller systems.
Mishra
Sabyashachi
S
Department of Chemistry, Technical University of Munich, D-85747 Garching, Germany. sabyashachi.mishra@ch.tum.de
Vallet
Valérie
V
Poluyanov
Leonid V
LV
Domcke
Wolfgang
W