Franck–Condon simulation of the photoelectron spectrum of including Duschinsky effects

Abstract: A theoretical method to calculate multidimensional Franck–Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectrum of the anion . Geometry optimizations and harmonic vibrational frequency calculations have been performed on the state of SO2 and state of . Franck–Condon analyses and spectral simulation were carried out on the first photoelectron band of . The theoretical spectra obtained by employing CCSD(T)/6-311+G(2d,p) values are in excellent agreement with the experiment. In addition, the equilibrium geometric parameters, r e(OS)=0.1508±0.0005 nm and θ e(O–S–O)=113.5±0.5°, of the state of , are derived by employing an iterative Franck–Condon analysis procedure in the spectral simulation. [Copyright &y& Elsevier]