Seminari: "Singling Out Dynamic and Nondynamic Correlation"






Dep. de Química Inorgànica i Orgànica


Sala d’Actes (Química-Física)

Conferenciant: Eduard Matito, Donostia International Physics Center (DIPC)

Resum: The correlation part of the pair density is separated into two components, one of them being predominant at short electronic ranges and the other at long ranges. The analysis of the intracular part of these components furnishes a natural partition of the Coulomb hole and it permits to classify molecular Systems according to the prevailing correlation: dynamic or nondynamic. The study of the long-range asymptotics reveals the key component of the pair density that is responsible for the description of London dispersion forces and a universal decay with the interelectronic distance. The application of these results to a two-electron two-atom model gives rise to indices of dynamic and nondynamic correlation based on natural orbital occupancies, which can be easily extended to provide a local picture of dynamic and nondynamic correlation. The natural range-separation, the identification of the dispersion forces, and the kind of predominant correlation type that arise from this analysis are expected to be important assets in the development of new electronic structure methods in wave function, density, and reduced density-matrix functional theories.