DUGi

Separation of dynamic and nondynamic correlation

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@298580

The account of electron correlation and its efficient separation into dynamic and nondynamic parts plays a key role in the development of computational methods. In this paper we suggest a physically-sound matrix formulation to split electron correlation into dynamic and nondynamic parts using the two-particle cumulant matrix and a measure of the deviation from idempotency of the first-order density matrix. These matrices are applied to a two-electron model, giving rise to a simplified electron correlation index that (i) depends only on natural orbitals and their occupancies, (ii) can be straightforwardly decomposed into orbital contributions and (iii) splits into dynamic and nondynamic correlation parts that (iv) admit a local version. These expressions are shown to account for dynamic and nondynamic correlation in a variety of systems containing different electron correlation regimes, thus providing the first separation of dynamic and nondynamic correlation using solely natural orbital occupancies

This research has been funded by the Spanish MINECO Projects No. CTQ2014-52525-P and CTQ2014-59212-P, and the Basque Country Consolidated Group Project No. IT588-13. ERC acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 660943

Royal Society of Chemistry (RSC)