Casimir–Polder Size Consistency: A Constraint Violated by Some Dispersion Theories
File version
Author(s)
Toulouse, Julien
Angyan, Janos G
Dobson, John F
Griffith University Author(s)
Primary Supervisor
Other Supervisors
Editor(s)
Date
Size
File type(s)
Location
License
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.
Journal Title
Journal of Chemical Theory and Computation
Conference Title
Book Title
Edition
Volume
13
Issue
12
Thesis Type
Degree Program
School
Publisher link
Patent number
Funder(s)
Grant identifier(s)
Rights Statement
Rights Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright 2017 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see 10.1021/acs.jctc.7b00996.
Item Access Status
Note
Access the data
Related item(s)
Subject
Software engineering
Theoretical and computational chemistry
Theoretical and computational chemistry not elsewhere classified
Biochemistry and cell biology
Physical chemistry