期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 120, 期 11, 页码 1763-1778出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b12335
关键词
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资金
- Distinguished Chair for Research Excellence in Chemistry
- National Center for Supercomputing Applications at the University of Illinois at Urbana-Champaign
In this article we describe the unique insights into the electronic structure of molecules provided by generalized valence bond (GVB) theory. We consider selected prototypical hydrocarbons as well as a number of hypervalent molecules and a set of first- and second-row valence isoelectronic species. The GVB wave function is obtained by variationally optimizing the orbitals and spin coupling in the valence bond wave function. The GVB wave function is a generalization of the Hartree-Fock (HF) wave function, lifting the double occupancy restriction on a subset of the HF orbitals as well as the associated orthogonality and spin coupling constraints. The GVB wave function includes a major fraction (if not all) of the nondynamical correlation energy of a molecule. Because of this, GVB theory properly describes bond formation and can answer one of the most compelling questions in chemistry: How are atoms changed by molecular formation? We show that GVB theory provides a unified description of the nature of the bonding in all of the above molecular species as well as contributing new insights into the well-known, but poorly understood, first-row anomaly.
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