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Title: Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional

Abstract

Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yields improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (αSX) are determined self-consistently, and those where αSX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G0W0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [2]
+ Show Author Affiliations
  1. Univ. of Chicago, Chicago, IL (United States)
  2. Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1389645
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 13; Journal Issue: 7; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Brawand, Nicholas P., Govoni, Marco, Vörös, Márton, and Galli, Giulia. Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b00368.
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Brawand, Nicholas P., Govoni, Marco, Vörös, Márton, & Galli, Giulia. Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional. United States. https://doi.org/10.1021/acs.jctc.7b00368
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Brawand, Nicholas P., Govoni, Marco, Vörös, Márton, and Galli, Giulia. Wed . "Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional". United States. https://doi.org/10.1021/acs.jctc.7b00368. https://www.osti.gov/servlets/purl/1389645.
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@article{osti_1389645,
title = {Performance and Self-Consistency of the Generalized Dielectric Dependent Hybrid Functional},
author = {Brawand, Nicholas P. and Govoni, Marco and Vörös, Márton and Galli, Giulia},
abstractNote = {Here, we analyze the performance of the recently proposed screened exchange constant functional (SX) on the GW100 test set, and we discuss results obtained at different levels of self-consistency. The SX functional is a generalization of dielectric dependent hybrid functionals to finite systems; it is nonempirical and depends on the average screening of the exchange interaction. We compare results for ionization potentials obtained with SX to those of CCSD(T) calculations and experiments, and we find excellent agreement, on par with recent state of the art methods based on many body perturbation theory. Applying SX perturbatively to correct PBE eigenvalues yields improved results in most cases, except for ionic molecules, for which wave function self-consistency is instead crucial. Calculations where wave functions and the screened exchange constant (αSX) are determined self-consistently, and those where αSX is fixed to the value determined within PBE, yield results of comparable accuracy. Perturbative G0W0 corrections of eigenvalues obtained with self-consistent αSX are small on average, for all molecules in the GW100 test set.},
doi = {10.1021/acs.jctc.7b00368},
journal = {Journal of Chemical Theory and Computation},
number = 7,
volume = 13,
place = {United States},
year = {Wed May 24 00:00:00 EDT 2017},
month = {Wed May 24 00:00:00 EDT 2017}
}
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