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A Priori Geometry Predictions

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Applications of Electronic Structure Theory

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

Abstract

Early quantum mechanical computations on the electronic structure of molecules were generally concerned with the determination of a wave function for a single assumed nuclear geometry (usually an experimentally determined equilibrium structure). As techniques have improved, however, it has increasingly become possible to make explorations of potential surfaces (total energies for heavy nuclei in the Born-Oppenheimer approximation) and hence to use theory directly to locate the minima in such surfaces and the corresponding equilibrium structural parameters. Such explorations can either be carried out partially, that is assuming some parameters and varying others (as in the study of “rigid” internal rotation with fixed bond lengths and angles) or, more desirably, by complete minimization of the energy with respect to all variables. Given the quantum mechanical procedure, the latter leads to a priori predictions of structure making no appeal to experimental data other than using the values of fundamental constants. Theoretical structures of this sort have been used for two main purposes. The first is to assess how well experimentally known structures are reproduced at a given level of theory and hence evaluate the limitations of the theory in a systematic manner. Second, the theory has been increasingly used to investigate structures of molecules for which experimental data are insufficient. Many such predictions have been made and there is an increasing number of examples of subsequent experimental verification.

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  1. Department of Chemistry, Carnegie-Mellon University, Pittsburgh, Pennsylvania, USA

    J. A. Pople

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  1. University of California, Berkeley, USA

    Henry F. Schaefer III

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© 1977 Plenum Press, New York

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Pople, J.A. (1977). A Priori Geometry Predictions. 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_1

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  • DOI: https://doi.org/10.1007/978-1-4684-8541-7_1

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