Low-energy excited states of divanadium: a matrix isolation and MRCI study

Abstract

The ground and excited electronic states of the vanadium dimer (V₂) have been studied using Ne matrix isolation experiments and quantum chemical calculations (multireference configuration interaction based on complete active space self-consistent orbitals). In the near infrared absorption spectrum, two vibrational progressions of a new electronic term with a large number of members have been observed with the origin at 1.08 eV and a fundamental vibrational quantum of 475 cm⁻¹. With the aid of calculations, it has been assigned to a ³Π_u electronic term. The calculations yield potential energy curves for a large number of singlet, triplet, and quintet electronic terms.