Valence Excited States of N2, CO, and BF

Abstract

Excitation energies and other spectroscopic constants (r_e, ω_e, ω_ex_e, B_e) are computed for excited electronic valence states of N₂, CO, and BF and their singly positive ions. The states considered are the lowest states of symmetry ¹Σ⁻, ¹Δ, ¹Π, ³Π, ³Σ⁺, ³Δ, ³Σ⁻ for the molecules and ²Σ⁺, ²Π for the ions. Approximate ground‐state Hartree—Fock molecular orbitals and the first unoccupied π orbital obtained by diagonalizing the ground‐state one‐electron Hamiltonian in a limited orbital basis set are used to construct electronic wavefunctions of the correct symmetry for each excited state. Electric dipole moments and dipole‐moment derivatives are computed. The computed Σ and Δ states of BF lie above the first ionization limit and are not expected to represent observable physical states. Computed spectroscopic constants for the other states considered are compared with observed data.