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σ-空穴键合:一种物理解释。

σ-Hole bonding: a physical interpretation.

作者信息

Politzer Peter, Murray Jane S, Clark Timothy

机构信息

Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA,

出版信息

Top Curr Chem. 2015;358:19-42. doi: 10.1007/128_2014_568.

Abstract

The anisotropic electronic densities of covalently-bonded Group IV-VII atoms frequently give rise to regions of positive electrostatic potential on the extensions of covalent bonds to these atoms. Through such positive "σ-holes," the atoms can interact attractively and highly directionally with negative sites such as the lone pairs of Lewis bases, anions, π electrons, etc. In the case of Group VII this is called "halogen bonding." Hydrogen bonding can be viewed as a less directional subset of σ-hole interactions. Since positive σ-holes often exist in conjunction with regions of negative potential, the atoms can also interact favorably with positive sites. In accordance with the Hellmann-Feynman theorem, all of these interactions are purely Coulombic in nature (which encompasses polarization and dispersion). The strength of σ-hole bonding increases with the magnitudes of the potentials of the positive σ-hole and the negative site; their polarizabilities must sometimes also be taken explicitly into account.

摘要

共价键合的IV - VII族原子的各向异性电子密度常常在与这些原子的共价键延伸方向上产生正静电势区域。通过这些正的“σ空穴”,这些原子能够与负性位点(如路易斯碱的孤对电子、阴离子、π电子等)发生吸引性且高度定向的相互作用。对于VII族元素,这种作用被称为“卤键”。氢键可被视为σ空穴相互作用中方向性较弱的一个子集。由于正的σ空穴常常与负电势区域共存,这些原子也能够与正性位点发生有利的相互作用。根据赫尔曼 - 费曼定理,所有这些相互作用本质上都是纯粹的库仑作用(包括极化和色散)。σ空穴键合的强度随着正σ空穴和负性位点电势大小的增加而增强;有时还必须明确考虑它们的极化率。

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