Ab initio calculations on the [formula omitted] → [formula omitted] photoelectron spectrum of thioformaldehyde negative ion

Abstract

The equilibrium structures, multidimensional potential energy surfaces, and anharmonic vibrational frequencies of thioformaldehyde (H2CS) and its 2B1 radical anion were obtained at the (U)CCSD(T)-F12a/cc-pVTZ-F12 level; and the photoelectron spectrum of H2CS−X∼2B1→ H2CS X∼1A1 was simulated by calculating the Franck-Condon factors (FCFs). The additional electrons cause a significant change in the bond length of the C = S bond of H2CS, which affects the potential energy surface and the C = S bond stretching mode, while the interaction between electrons turns the originally planar structure of H2CS into a slightly out-of-plane umbrella structure, resulting in an unusual change in the vibrational frequency of the out-of-plane bending mode. Finally, a time-independent eigenstate-free Raman wave function approach (RWF) was used to calculate the photoelectron spectrum of H2CS and to point out the changes in the band under the influence of different temperatures. These data provides a theoretical basis for interstellar observations and experimental studies.