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AB Initio Energy Derivatives Calculated Analytically

  • Conference paper
Computational Theoretical Organic Chemistry

Part of the book series: NATO Advanced Study Institutes Series ((ASIC,volume 67))

Abstract

The efficiency and accuracy of analytical differentiation in ab initio calculations are compared with the numerical approach. Formulae for computing integral derivatives are developed and the expression for the first derivative of the SCF energy is presented. The coupled-perturbed Hartree-Fock equations are solved for the first derivative of the molecular orbital coefficients. These are then used to calculate the second derivative of the SCF energy and the first derivatives of two energy schemes involving electron correlation: second order Møller-Plesset and all-doubles configuration interaction-Timing data indicate that as much as an order of magnitude increase in efficiency can be obtained through the use of derivative methods. Examples of geometry optimization and vibrational frequency calculation are given; additional applications to NMR magnetic shielding and electric polarizibility are discussed briefly.

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Author information

Authors and Affiliations

  1. Merck Sharp & Dohme Research Laboratories, Rahway, New Jersey, 07065, USA

    H. Bernhard Schlegel

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  1. H. Bernhard Schlegel
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Editor information

Editors and Affiliations

  1. Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

    I. G. Csizmadia

  2. Centre de Mécanique Ondulatoire Appliquée, Centre National de la Recherche Scientifique, Paris, France

    R. Daudel

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© 1981 D. Reidel Publishing Company, Dordrecht, Holland

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Bernhard Schlegel, H. (1981). AB Initio Energy Derivatives Calculated Analytically. In: Csizmadia, I.G., Daudel, R. (eds) Computational Theoretical Organic Chemistry. NATO Advanced Study Institutes Series, vol 67. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-8472-1_7

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  • DOI: https://doi.org/10.1007/978-94-009-8472-1_7

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-009-8474-5

  • Online ISBN: 978-94-009-8472-1

  • eBook Packages: Springer Book Archive

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