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

2017/11/23 by Tim Gould, Julien Toulouse, Gould, Tim +5
Physics and Astronomy · #Chemical Physics (physics.chem-ph) #Computational Physics (physics.comp-ph) #FOS: Physical sciences #Mechanical and Optical Resonators #Quantum Electrodynamics and Casimir Effect #Quantum Mechanics and Applications

paper · pdf · doi:10.48550/arxiv.1711.08727

openalex publication_date 2017/11/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

A key goal in quantum chemistry methods, whether ab initio or otherwise, is\nto achieve size consistency. In this manuscript we formulate the related idea\nof "Casimir-Polder size consistency" that manifests in long-range dispersion\nenergetics. We show that local approximations in time-dependent density\nfunctional theory dispersion energy calculations violate the consistency\ncondition because of incorrect treatment of highly non-local "xc kernel"\nphysics, by up to 10% in our tests on closed-shell atoms.\n

Citations

• Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism
• Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction
• A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
• Accurate description of van der Waals complexes by density functional theory including empirical corrections
• Prediction of Dispersion Forces: Is There a Problem?

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