Theoretical support for the latest assignment of the electronic spectrum of [CrOCl4]–

Abstract

Optimised basis set discrete variational Xα self-consistent charge calculations of the electronic spectrum for the [CrOCl₄]^– ion have been performed. The agreement between observed and calculated d–d and charge-transfer transition energies is excellent. The first two absorption bands are definitely calculated to be d–d in origin. This agrees with the latest assignment, based on a reinvestigation of the low-temperature polarised absorption spectrum, and refutes earlier suggestions based on ab initio configuration interaction and multiple scattering Xα computations.