Electron Delocalization Range in Atoms and on Molecular Surfaces

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• 作者：Benjamin G. Janesko ; Kenneth B. Wiberg ; Giovanni Scalmani ; Michael J. Frisch
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：July 12, 2016
• 年：2016
• 卷：12
• 期：7
• 页码：3185-3194
• 全文大小：575K
• 年卷期：0
• ISSN：1549-9626

文摘

The electron delocalization range function EDR(r⃗; d) (J. Chem. Phys. 2014, 141, 144104) quantifies the extent to which an electron at point r⃗ in a calculated wave function delocalizes over distance d. This work illustrates how atomic averages of the EDR, and plots of the EDR on molecule surfaces, provide a chemically intuitive picture of the sizes of occupied orbital lobes in different regions. We show how the surface and atomic delocalization distinguish aminophosphine ligand’s hard N and soft P lone pairs, distinguish the site preference for Ag⁺ cation binding to conjugated oligomers, and provide information that is different from and complementary to conjugation lengths. Applications to strong correlation and the prototropic tautomerization of phosphinylidenes R₁R₂HPO illustrates how the surface and atomic delocalization can work with other tools to provide a nuanced picture of reactivity.