English

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

Chemical Physics 2017-11-27 v1 Computational Physics

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.

Keywords

Cite

@article{arxiv.1711.08727,
  title  = {Casimir-Polder size consistency -- a constraint violated by some dispersion theories},
  author = {Tim Gould and Julien Toulouse and János Ángyán and John F. Dobson},
  journal= {arXiv preprint arXiv:1711.08727},
  year   = {2017}
}

Comments

Journal of Chemical Theory and Computation, American Chemical Society, 2017