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Supercomputer Algorithms for Reactivity, Dynamics and Kinetics of Small Molecules pp 23–36Cite as

Modern Electronic Structure Calculations: The Accurate Prediction of Spectroscopic Band Origins

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Part of the book series: NATO ASI Series ((ASIC,volume 277))

Abstract

Derivative theory has been one of major advances in quantum chemistry in recent years, enabling the quantum chemist to make valuable predictions in the area of microwave and infrared spectroscopy. Here it is argued that a high accuracy model for predictive quantum chemistry is MP2 with sufficiently large basis sets (TZ2p+ f), for which it is possible today to calculate analytic second derivatives. Harmonic frequencies are often accurate to 1% in this model. If analytic SCF third derivatives together with finite difference fourth derivatives are also available, it is then possible to extend the model to the prediction of band origins. Small scaling procedures are suggested which yield an accuracy of the order of 15cm-1. Supporting calculations are presented, including an incomplete study of H2O2.

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Author information

Authors and Affiliations

  1. University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, UK

    Nicholas C. Handy

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  1. Nicholas C. Handy
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Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Perugia, Perugia, Italy

    Antonio Laganà

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© 1989 Kluwer Academic Publishers

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Handy, N.C. (1989). Modern Electronic Structure Calculations: The Accurate Prediction of Spectroscopic Band Origins. In: Laganà, A. (eds) Supercomputer Algorithms for Reactivity, Dynamics and Kinetics of Small Molecules. NATO ASI Series, vol 277. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0945-8_2

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  • DOI: https://doi.org/10.1007/978-94-009-0945-8_2

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6915-1

  • Online ISBN: 978-94-009-0945-8

  • eBook Packages: Springer Book Archive

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