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Casimir-Polder Size Consistency: A Constraint Violated by Some Dispersion Theories
Tim Gould1, Julien Toulouse2, János G Ángyán3
1Queensland Micro- and Nanotechnology Centre, Griffith University , Nathan, Queensland 4111, Australia.
Abstract:
A key goal in quantum chemistry methods, whether ab initio or otherwise, is to achieve size consistency. In this work 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 nonlocal "xc kernel" physics, by up to 10% in our tests on closed-shell atoms.
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