Franck-Condon simulation of photoelectron spectroscopy of HNO~- and DNO~- : including Duschinsky effects

摘要

A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectra of HNO~- and DNO~- radicals. Geometry optimization and harmonic vibrational frequency calculations have been performed on the X-tilde ~1A' and a-tilde ~3A" states of HNO/DNO and X-tilde ~2A" state of HNO~-/DNO~-. The theoretical spectra obtained by employing B3LYP/6-311+G(2d,p) values are in excellent agreement with the observed ones. In addition, the equilibrium geometry parameters, R(NO) = 0.1335 ± 0.0005 nm, ∠(HNO) = 106.3°± 0.5°, of the X-tilde ~2A" state of HNO~-/DNO~- are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.