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Molecular Fine Structure

  • Chapter
Applications of Electronic Structure Theory

Part of the book series: Modern Theoretical Chemistry ((MTC,volume 4))

Abstract

Weak interactions in the complete many-body Hamiltonian are an important part of modern chemical theory and experiment.(1) As we have seen in this volume, these terms are usually neglected in the construction of electronic wave functions because they account for relatively small amounts of energy, typically on the order of cm-1. Nevertheless, they can be measured to very high accuracy, such as in EPR experiments that probe the coupling of the electron spins with themselves and with the angular momenta of their orbital motion.(2,3) These particular interactions, which are the subject of this chapter, are so small that they act as perturbations to split the nonrelativistic electronic states into a “fine structure” of levels. Since the spacings between these spin multiplets are often very sensitive to the details of the charge distribution, they provide a test of the zero-order wave functions that are used to calculate them.* We are, therefore, dealing with weak forces that have conspicious, measurable, and calculable effects.

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Authors and Affiliations

  1. Battelle Columbus Laboratories, Columbus, Ohio, USA

    Stephen R. Langhoff

  2. Department of Chemistry, Battelle Columbus Laboratories and The Ohio State University, Columbus, Ohio, USA

    C. William Kern

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  1. Stephen R. Langhoff
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  1. University of California, Berkeley, USA

    Henry F. Schaefer III

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Langhoff, S.R., Kern, C.W. (1977). Molecular Fine Structure. In: Schaefer, H.F. (eds) Applications of Electronic Structure Theory. Modern Theoretical Chemistry, vol 4. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-8541-7_10

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