Role of s-p Orbital Mixing in the Bonding and Properties of Second-Period Diatomic Molecules

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• 作者：F. Matthias Bickelhaupt ; Jeffrey K. Nagle ; William L. Klemm
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：March 20, 2008
• 年：2008
• 卷：112
• 期：11
• 页码：2437 - 2446
• 全文大小：418K
• 年卷期：v.112,no.11(March 20, 2008)
• ISSN：1520-5215

文摘

Qualitative molecular orbital theory is widely used as a conceptual tool to understand chemical bonding.Symmetry-allowed orbital mixing between atomic or fragment orbitals of different energies can greatlycomplicate such qualitative interpretations of chemical bonding. We use high-level Amsterdam DensityFunctional calculations to examine the issue of whether orbital mixing for some familiar second-rowhomonuclear and heteronuclear diatomic molecules results in net bonding or antibonding character for agiven molecular orbital. Our results support the use of slopes of molecular orbital energy versus bond distanceplots (designated radial orbital-energy slope: ROS) as the most useful criterion for making this determination.Calculated atomic charges and frontier orbital properties of these molecules allow their acid-base chemistry,including their reactivities as ligands in coordination chemistry, to be better understood within the context ofthe Klopman interpretation of hard and soft acid-base theory. Such an approach can be extended to anymolecular species.