Zero-Flux Surfaces of the Electrostatic Potential: The Border of Influence Zones of Nucleophilic and Electrophilic Sites in Crystalline Environment

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• 作者：Ignasi Mata ; Elies Molins ; Enrique Espinosa
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：October 4, 2007
• 年：2007
• 卷：111
• 期：39
• 页码：9859 - 9870
• 全文大小：1303K
• 年卷期：v.111,no.39(October 4, 2007)
• ISSN：1520-5215

文摘

The topology of the electrostatic potential (r) has been studied for single molecules using geometries andelectron distributions (r) determined from high-resolution single-crystal X-ray diffraction data. The electrostaticpotential gradient (r), which is the negative of the electric field E = -, has been represented, revealingthe position of zero-flux surfaces and critical points. Local maxima and minima of the electrostatic potentialare interpreted in terms of electrophilic and nucleophilic sites, which present influence zones delimited byzero-flux surfaces containing saddle points. The influence zones of the nucleophilic and electrophilic sitesdefine two alternative partitions of the space in disjoint volumes, the completeness of these partitions dependingon either the neutral or ionic character of the molecule. The results obtained by using this methodology areuseful for the interpretation of the saddle points of the electrostatic potential, which are related to the limitsof the influence zones and reveal the path for preferred attack on reactive sites with finite influence zones.