Modeling the Photoelectron Spectra of MoNbO₂^– Accounting for Spin Contamination in Density Functional Theory

Abstract

Spin contamination in density functional studies has been identified as a cause of discrepancies between theoretical and experimental spectra of metal oxide clusters such as MoNbO2. We perform calculations to simulate the photoelectron spectra of the MoNbO2 anion using broken-symmetry density functional theory incorporating recently developed approximate projection methods. These calculations are able to account for the presence of contaminating spin states at single-reference computational cost. Results using these new tools demonstrate the significant effect of spin-contamination on geometries and force constants and show that the related errors in simulated spectra may be largely overcome by using an approximate projection model.