Toward a physical understanding of electron-sharing two-center bonds. I. General aspects

被引:64
作者
Bitter, T.
Ruedenberg, K.
Schwarz, W. H. E. [1 ]
机构
[1] Univ Siegen, D-57068 Siegen, Germany
[2] Ernst Klett Verlag, D-70178 Stuttgart, Germany
[3] Shanghai Jiao Tong Univ, Shanghai 200240, Peoples R China
关键词
bond types; covalence; polar bond; bond energy analysis; diatomics; effective core potentials; pseudopotentials;
D O I
10.1002/jcc.20531
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In 1916, Lewis and Kossel laid the empirical ground for the electronic theory of valence, whose quantum theoretical foundation was uncovered only slowly. We can now base the classification of the various traditional chemical bond types in a threefold manner on the one- and two-electron terms of the quantum-physical Hamiltonian (kinetic, atomic core attraction, electron repulsion). Bond formation is explained by splitting up the real process into two physical steps: (i) interaction of undeformed atoms and (ii) relaxation of this nonstationary system. We aim at a flexible bond energy partitioning scheme that can avoid cancellation of large terms of opposite sign. The driving force of covalent bonding is a lowering of the quantum kinetic energy density by sharing. The driving force of heteropolar bonding is a lowering of potential energy density by charge rearrangement in the valence shell. Although both mechanisms are quantum mechanical in nature, we can easily visualize them, since they are of one-electron type. They are however tempered by two-electron correlations. The richness of chemistry, owing to the diversity of atomic cores and valence shells, becomes intuitively understandable with the help of effective core pseudopotentials for the valence shells. Common conceptual difficulties in understanding chemical bonds arise from quantum kinematic aspects as well as from paradoxical though classical relaxation phenomena. On this conceptual basis, a dozen different bond types in diatomic molecules will be analyzed in the following article. We can therefore examine common features as well as specific differences of various bonding mechanisms. (C) 2006 Wiley Periodicals, Inc.
引用
收藏
页码:411 / 422
页数:12
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