skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Assessment of a long-range corrected hybrid functional

Abstract

Common approximate exchange-correlation functionals suffer from self-interaction error, and as a result, their corresponding potentials have incorrect asymptotic behavior. The exact asymptote can be imposed by introducing range separation into the exchange component and replacing the long-range portion of the approximate exchange by the Hartree-Fock counterpart. The authors show that this long-range correction works particularly well in combination with the short-range variant of the Perdew-Burke-Ernzerhof (PBE) exchange functional. This long-range-corrected hybrid, here denoted LC-{omega}PBE, is remarkably accurate for a broad range of molecular properties, such as thermochemistry, barrier heights of chemical reactions, bond lengths, and most notably, description of processes involving long-range charge transfer.

Authors:
;  [1]
  1. Department of Chemistry, Rice University, Houston, Texas 77005 (United States)
Publication Date:
OSTI Identifier:
20864360
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 125; Journal Issue: 23; Other Information: DOI: 10.1063/1.2409292; (c) 2006 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BOND LENGTHS; CHARGE-EXCHANGE REACTIONS; CHEMICAL REACTIONS; CORRELATIONS; HARTREE-FOCK METHOD; HYBRIDIZATION; INTERACTIONS; REACTION KINETICS

Citation Formats

Vydrov, Oleg A., and Scuseria, Gustavo E. Assessment of a long-range corrected hybrid functional. United States: N. p., 2006. Web. doi:10.1063/1.2409292.
Vydrov, Oleg A., & Scuseria, Gustavo E. Assessment of a long-range corrected hybrid functional. United States. doi:10.1063/1.2409292.
Vydrov, Oleg A., and Scuseria, Gustavo E. Thu . "Assessment of a long-range corrected hybrid functional". United States. doi:10.1063/1.2409292.
@article{osti_20864360,
title = {Assessment of a long-range corrected hybrid functional},
author = {Vydrov, Oleg A. and Scuseria, Gustavo E.},
abstractNote = {Common approximate exchange-correlation functionals suffer from self-interaction error, and as a result, their corresponding potentials have incorrect asymptotic behavior. The exact asymptote can be imposed by introducing range separation into the exchange component and replacing the long-range portion of the approximate exchange by the Hartree-Fock counterpart. The authors show that this long-range correction works particularly well in combination with the short-range variant of the Perdew-Burke-Ernzerhof (PBE) exchange functional. This long-range-corrected hybrid, here denoted LC-{omega}PBE, is remarkably accurate for a broad range of molecular properties, such as thermochemistry, barrier heights of chemical reactions, bond lengths, and most notably, description of processes involving long-range charge transfer.},
doi = {10.1063/1.2409292},
journal = {Journal of Chemical Physics},
number = 23,
volume = 125,
place = {United States},
year = {Thu Dec 21 00:00:00 EST 2006},
month = {Thu Dec 21 00:00:00 EST 2006}
}
  • Bridging the gap between first principles methods and empirical schemes, the density functional based tight-binding method (DFTB) has become a versatile tool in predictive atomistic simulations over the past years. One of the major restrictions of this method is the limitation to local or gradient corrected exchange-correlation functionals. This excludes the important class of hybrid or long-range corrected functionals, which are advantageous in thermochemistry, as well as in the computation of vibrational, photoelectron, and optical spectra. The present work provides a detailed account of the implementation of DFTB for a long-range corrected functional in generalized Kohn-Sham theory. We apply themore » method to a set of organic molecules and compare ionization potentials and electron affinities with the original DFTB method and higher level theory. The new scheme cures the significant overpolarization in electric fields found for local DFTB, which parallels the functional dependence in first principles density functional theory (DFT). At the same time, the computational savings with respect to full DFT calculations are not compromised as evidenced by numerical benchmark data.« less
  • Previously proposed schemes of coupling short-range density-functional-based with long-range wave-function-based methods are tested for the notoriously difficult case of correctly describing the charge distribution in compounds containing late transition elements. We show that for the dipole moments of the group-11 transition metal hydrides and halides the recently developed Coulomb-attenuated Becke three-parameter Lee-Yang-Parr hybrid functional already leads to a substantial improvement compared to other density functionals. Further improvement is achieved by combining a gradient-corrected short-range functional of the Perdew-Burke-Ernzerhof type with coupled-cluster theory. The results clearly demonstrate that mixing of long-range ab initio Hartree-Fock and post-Hartree-Fock methods helps to remove deficienciesmore » of current density functionals.« less
  • We study the low-lying excited states of the zinc-porphyrin molecule in aqueous solution using long-range corrected TDDFT.We report results using the CAM-B3LYP and CAM-PBE0 functionals and compare them with previously reported excited states based on high-level coupled cluster (CC) methods. The aqueous environment is treated via a QM/MM approach.
  • In this work we present a study of the excitation energies of adenine, cytosine, guanine, thymine and the adenine-thymine (AT) and guanine-cytosine (GC) base pairs using long-range corrected (LC) density functional theory. We compare three recent LC-functionals, BNL, CAM-B3LYP and LC-PBE0 with B3LYP and coupled cluster results from the literature. We find that the best overall performance is for the BNL functional based on LDA. However, in order to achieve this good agreement a smaller attenuation parameter was needed which leads to non-optimum performance for ground state properties. B3LYP, on the other hand, severely underestimates the charge transfer (CT) transitionsmore » in the base pairs. Surprisingly we also find that the CAM-B3LYP functional also underestimates the CT excitation energy for the GC base pair, but correctly describes the AT base pair. This illustrates the importance of retaining the full long-range exact exchange even at distances as short as that of the DNA base pairs. The worst overall performance was obtained with the LC-PBE0 functional which overestimates the excitations for the individual bases as well as the base pairs. It is therefore crucial to strike a good balance between the amount of local and long-range exact exchange.« less
  • In this work we present a study of the excitation energies of adenine, cytosine, guanine, thymine and the adenine-thymine (AT) and guanine-cytosine (GC) base pairs using long-range corrected (LC) density functional theory. We compare three recent LC-functionals, BNL, CAM-B3LYP and LC-PBE0 with B3LYP and coupled cluster results from the literature. We find that the best overall performance is for the BNL functional based on LDA. However, in order to achieve this good agreement a smaller attenuation parameter was needed which leads to non-optimum performance for ground state properties. B3LYP, on the other hand, severely underestimates the charge transfer (CT) transitionsmore » in the base pairs. Surprisingly we also find that the CAM-B3LYP functional also underestimates the CT excitation energy for the GC base pair, but correctly describes the AT base pair. This illustrates the importance of retaining the full long-range exact exchange even at distances as short as that of the DNA base pairs. The worst overall performance was obtained with the LC-PBE0 functional which overestimates the excitations for the individual bases as well as the base pairs. It is therefore crucial to strike a good balance between the amount of local and long-range exact exchange.« less