Restoring Size Consistency of Approximate Functionals Constructed from the Adiabatic Connection

Abstract

Approximate exchange–correlation functionals built by modeling in a nonlinear way the adiabatic connection (AC) integrand of density functional theory have many attractive features, being virtually parameter-free and satisfying different exact properties, but they also have a fundamental flaw: they violate the size-consistency condition, crucial to evaluate interaction energies of molecular systems. We show that size consistency in the AC-based functionals can be restored in a very simple way at no extra computational cost. Results on a large set of benchmark molecular interaction energies show that functionals based on the interaction strength interpolation approximations are significantly more accurate than second-order perturbation theory.

Journal

Journal ID (nlm-ta): J Phys Chem Lett

Journal ID (iso-abbrev): J Phys Chem Lett

Journal ID (publisher-id): jz

Journal ID (coden): jpclcd

Title: The Journal of Physical Chemistry Letters

Publisher: American Chemical Society

ISSN (Electronic): 1948-7185

Publication date (Electronic): 22 May 2018

Publication date (Print): 07 June 2018

Volume: 9

Issue: 11

Pages: 3137-3142

Affiliations

[† ]Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, FEW, Vrije Universiteit , De Boelelaan 1083, 1081HV Amsterdam, The Netherlands

[‡ ]Institute for Microelectronics and Microsystems (CNR-IMM) , Via Monteroni, Campus Unisalento, 73100 Lecce, Italy

[§ ]Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia , Via Barsanti, I-73010 Arnesano, Italy

Author notes

[* ]E-mail: s.vuckovic@ 123456vu.nl .

Article

DOI: 10.1021/acs.jpclett.8b01054

PMC ID: 5994725

PubMed ID: 29787273

Copyright statement: Copyright © 2018 American Chemical Society

License:

This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License, which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes.

Categories

Subject: Letter

Custom metadata

document-id-old-9 jz8b01054

document-id-new-14 jz-2018-01054k

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