Structure of the Se Isomers─An Ab Initio Study.

This study investigates the equilibrium geometries of four different Se isomers using the coupled cluster single and double perturbative (CCSD(T)) method, extrapolating to the complete basis sets. The ground-state geometry of the Se isomer with the C structure (2.8715 Å, 2.1750 Å, and 88.4°) is found to be very close to other theoretical values (2.910 Å, 2.224 Å, and 90.0°) for the Se═Se and Se-Se bond lengths and valence angle. Additionally, the adiabatic electron affinity, vertical electron affinity, and vertical ionization energy are calculated. The multireference configuration interaction method was used to calculate transitions from the singlet ground state to some excited counterparts, including the vertical excitation energy, oscillator strength, and main electronic configuration. The predicted wavelengths of electronic transitions to 1B, 1A with C symmetry, and 1B state with the C symmetry could match the experimental NIR absorption band at 710-850 nm. These transitions and electronic properties may provide insights into the role of selenium in astrophysical environments, where Se in the solar system has been confirmed to originate from the supernova explosion process. The theoretical results offer a deeper understanding of Se electronic and geometric structures while also providing crucial spectroscopic data that could aid in the identification of selenium-containing molecules in extraterrestrial environments.