Oxygen Monofluoride (OF, 2π): Hartree–Fock Wavefunction, Binding Energy, Ionization Potential, Electron Affinity, Dipole and Quadrupole Moments, and Spectroscopic Constants. A Comparison of Theoretical and Experimental Results

Abstract

Self‐consistent‐field wavefunctions near the Hartree–Fock limit have been calculated by the Roothaan expansion method for OF(²π) at several internuclear separations; the total energy at the Hartree–Fock minimum (1.321 Å) was found to be − 174.19502 hartree. Based on the assumption that the correlation energy was approximately the same as for O₂⁻, and also by interpolating the correlation energy of OF across the CF, NF, OF, and F₂ sequence, the binding energy $\mathrm{D(}\mathrm{OF})$ was deduced to be 3.0^+0.3_−0.8 eV. A Dunham analysis of the potential‐energy curve gave values for the various spectroscopic constants. In addition, the ionization potential and electron affinity for the vertical processes, and the dipole and quadrupole moments of OF⁺(³Σ), OF(²π), and OF⁻(¹Σ) were also calculated.