Fractional charge behavior and band gap predictions with the XYG3 type of doubly hybrid density functionals

In this work, we examine the fractional charge behaviors of doubly hybrid (DH) functionals. By plotting the ground-state energies E and energy derivatives for atoms and molecules with fractional electron numbers N, we directly quantify the delocalization errors of some representative DH functionals...

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Vydané v:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Ročník 118; číslo 39; s. 9201
Hlavní autori: Su, Neil Qiang, Yang, Weitao, Mori-Sánchez, Paula, Xu, Xin
Médium: Journal Article
Jazyk:English
Vydavateľské údaje: United States 02.10.2014
ISSN:1520-5215, 1520-5215
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Shrnutí:In this work, we examine the fractional charge behaviors of doubly hybrid (DH) functionals. By plotting the ground-state energies E and energy derivatives for atoms and molecules with fractional electron numbers N, we directly quantify the delocalization errors of some representative DH functionals such as B2PLYP, XYG3, and XYGJ-OS. Numerical assessments on ionization potentials (IPs), electron affinities (EAs), and fundamental gaps, from either integer number calculations or energy derivative calculations, are provided. It is shown that the XYG3 type of DH functionals gives good agreement between their energy derivatives and the experimental IPs, EAs, and gaps, as expected from their nearly straight line fractional charge behaviors.
Bibliografia:ObjectType-Article-1
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ISSN:1520-5215
1520-5215
DOI:10.1021/jp5029992