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