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Author Lutsker, V. ♦ Niehaus, T. A. ♦ Aradi, B.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ AFFINITY ♦ BENCHMARKS ♦ COMPARATIVE EVALUATIONS ♦ DENSITY FUNCTIONAL METHOD ♦ ELECTRIC FIELDS ♦ FUNCTIONALS ♦ IMPLEMENTATION ♦ IONIZATION POTENTIAL ♦ MOLECULES ♦ THERMOCHEMICAL DIAGRAMS ♦ THERMOCHEMICAL PROCESSES
Abstract 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 the 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.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2015-11-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 143
Issue Number 18


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