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Speaker: James Shee, UC Berkeley
Title: Revealing the nature of electron correlation in transition metal complexes with symmetry-breaking and chemical intuition
Abstract: I will describe a framework through which theoreticians and practicing computational chemists alike can view electron correlations in molecular transition metal complexes. Static correlation is presented from the perspective of simple chemical models such as ligand-field and molecular orbital theories, and an analysis of symmetry breaking suggests that it is rarely encountered in thermochemical calculations of realistic transition metal compounds (though we do reveal a few important situations in which it is relevant). The relative complexity of transition metal bonding, relative to that of typical organic compounds, places a larger burden on a theory's treatment of dynamic correlation. After recognizing that typical bonds in organometallic complexes can be viewed as a correlated interaction involving multiple electron pairs, we demonstrate that MP2 and related double hybrid density functionals fail to describe this type of bonding. Indeed, a theory’s description of dynamic correlation, which affects relative spin-state energetics and thus spin-symmetry breaking, is found to govern the efficacy of its use to diagnose static correlation.