文章基本信息

标题：Energy decomposition analysis of single bonds within Kohn–Sham density functional theory
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作者：Daniel S. Levine ; Martin Head-Gordon
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2017
卷号：114
期号：48
页码：12649-12656
DOI：10.1073/pnas.1715763114
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn–Sham density functional theory based on spin projection equations that are exact within wave function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree–Fock results. Substituent effects are illustrated by comparing the C–C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal–metal bonds in experimentally characterized compounds are examined: a Mg I – Mg I dimer, the Zn I – Zn I bond in dizincocene, and the Mn–Mn bond in dimanganese decacarbonyl.
关键词：energy decomposition analysis ; chemical bonding ; density functional theory ; covalent bonds ; charge-shift bonds