Role of s-p orbital mixing in the bonding and properties of second-period diatomic molecules

F.M. Bickelhaupt, J.K. Nagle, W.L. Klemm

Research output: Contribution to JournalArticleAcademicpeer-review


Qualitative molecular orbital theory is widely used as a conceptual tool to understand chemical bonding. Symmetry-allowed orbital mixing between atomic or fragment orbitais of different energies can greatly complicate such qualitative interpretations of chemical bonding. We use high-level Amsterdam Density Functional calculations to examine the issue of whether orbital mixing for some familiar second-row homonuclear and heteronuclear diatomic molecules results in net bonding or antibonding character for a given molecular orbital. Our results support the use of slopes of molecular orbital energy versus bond distance plots (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 of the Klopman interpretation of hard and soft acid-base theory. Such an approach can be extended to any molecular species. © 2008 American Chemical Society.
Original languageEnglish
Pages (from-to)2437-2446
Number of pages10
JournalJournal of Physical Chemistry A
Issue number11
Early online date28 Feb 2008
Publication statusPublished - 1 Mar 2008


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