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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| Published in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 118; no. 39; p. 9201 |
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| Main Authors: | , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
02.10.2014
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| ISSN: | 1520-5215, 1520-5215 |
| Online Access: | Get more information |
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| Summary: | 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. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1520-5215 1520-5215 |
| DOI: | 10.1021/jp5029992 |