期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 114, 期 48, 页码 12649-12656出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1715763114
关键词
energy decomposition analysis; chemical bonding; density functional theory; covalent bonds; charge-shift bonds
资金
- US National Science Foundation [CHE-1665315, CHE-1363342]
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.
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