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Casimir-Polder size consistency -- a constraint violated by some dispersion theories

Authors :
Gould, Tim
Toulouse, Julien
Ángyán, János
Dobson, John F.
Publication Year :
2017

Abstract

A key goal in quantum chemistry methods, whether ab initio or otherwise, is to achieve size consistency. In this manuscript we formulate the related idea of "Casimir-Polder size consistency" that manifests in long-range dispersion energetics. We show that local approximations in time-dependent density functional theory dispersion energy calculations violate the consistency condition because of incorrect treatment of highly non-local "xc kernel" physics, by up to 10% in our tests on closed-shell atoms.<br />Comment: Journal of Chemical Theory and Computation, American Chemical Society, 2017

Details

Database :
arXiv
Publication Type :
Report
Accession number :
edsarx.1711.08727
Document Type :
Working Paper