Assessment of the exchange-correlation functionals for the physical description of spin transition phenomena by density functional theory methods: all the same?

Samir Zein; Serguei A Borshch; Paul Fleurat-Lessard; Mark E Casida; Henry Chermette

doi:10.1063/1.2406067

Assessment of the exchange-correlation functionals for the physical description of spin transition phenomena by density functional theory methods: all the same?

J Chem Phys. 2007 Jan 7;126(1):014105. doi: 10.1063/1.2406067.

Authors

Samir Zein¹, Serguei A Borshch, Paul Fleurat-Lessard, Mark E Casida, Henry Chermette

Affiliation

¹ Laboratoire de Chimie, UMR CNRS 5182, Ecole Normale Supérieure de Lyon, 46 allée d'Italie, 69364 Lyon Cedex 07, France.

PMID: 17212488
DOI: 10.1063/1.2406067

Abstract

This study aims to assess present day density functionals in the description of spin crossover iron(II) complexes. Two recently synthesized spin crossover complexes were considered. Theoretical calculations were made using 53 of the most popular exchange-correlation density functionals with triple zeta plus polarization quality basis sets. The present work shows that even though different density functionals can lead to different energy gaps between spin states, most of them are very similar for these two compounds when a comparison between energy gaps is sought. The present work shows that even though different exchange correlations can lead to different energy gaps between spin states, the difference between these gaps calculated at different geometries and that calculated at a given reference geometry is surprisingly independent of the choice of functional. The reasons for the similarities and the differences among exchange and correlation functional combinations are discussed.