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Theoretical thermochemistry of radicals
Book chapter

Theoretical thermochemistry of radicals

D.J. Henry and L. Radom
Quantum-Mechanical Prediction of Thermochemical Data, pp.161-197
Kluwer Academic Publishers
2001
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Abstract

Introduction In general, radicals are highly reactive species and can therefore often be difficult to study experimentally. Nevertheless, there is a number of experimental procedures that can he used to determine radical thermochemistry, either directly or indirectly (e.g. through thermochemical cycles. Berkowitz, Ellison and Gutman have reviewed several of these methods and noted their strengths and limitations. Developments in computer technology mean that ab initio molecular orbital theory now provides a viable alternative source of quantitative gas- phase thermochemical information. However, the theoretical treatment of open-shell systems such as radicals presents its own difficulties. Therefore, the accurate prediction of radical thermochemistry with theoretical procedures poses an interesting challenge. In this chapter, we look closely at the performance of several ab initio techniques in the prediction of radical thermochemistry with the aim of demonstrating which procedures are best suited in representative situations. We restrict our attention to several areas in which we have had a recent active interest, namely, the determination of radical heats of formation, bond dissociation energies (BDEs), radical stabilization energies (RSEs), and selected radical reaction barriers end reaction enthalpies. We focus particularly on the results of our recent studies.

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