期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 32, 页码 10282-10291出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b05600
关键词
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资金
- Energy Frontier Research in Extreme Environments (EFree) Center, an Energy Frontier Research Center - US Department of Energy, Office of Science [DE-SC00010.57]
- National Science Foundation (NSF) [CHE 13-05872]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1305872] Funding Source: National Science Foundation
Following the work of L. C. Allen, this work begins by relating the central chemical concept of electronegativity with the average binding energy of electrons in a system. The average electron binding energy, (chi) over bar, is in principle accessible from experiment, through photoelectron and X-ray spectroscopy. It can also be estimated theoretically. (chi) over bar has a rigorous and understandable connection to the total energy. That connection defines a new kind of energy decomposition scheme. The changing total energy in a reaction has three primary contributions to it: the average electron binding energy, the nuclear nuclear repulsion, and multielectron interactions. This partitioning allows one to gain insight into the predominant factors behind a particular energetic preference. We can conclude whether an energy change in a transformation is favored or resisted by collective changes to the binding energy of electrons, the movement of nuclei, or multielectron interactions. For example, in the classical formation of H-2 from atoms, orbital interactions dominate nearly canceling nuclear nuclear repulsion and two-electron interactions. While in electron attachment to an H atom, the multielectron interactions drive the reaction. Looking at the balance of average electron binding energy, multielectron, and nuclear nuclear contributions one can judge when more traditional electronegativity arguments can be justifiably invoked in the rationalization of a particular chemical event.
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