Self‐Consistent Procedures for Generalized Valence Bond Wavefunctions. Applications H_3, BH, H_(2)O, C_(2)H_6, and O_2

Hunt, W. J. and Hay, P. J. and Goddard, W. A., III (1972) Self‐Consistent Procedures for Generalized Valence Bond Wavefunctions. Applications H_3, BH, H_(2)O, C_(2)H_6, and O_2. Journal of Chemical Physics, 57 (2). pp. 738-748. ISSN 0021-9606. doi:10.1063/1.1678308. https://resolver.caltech.edu/CaltechAUTHORS:20120727-105852837

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Abstract

Methods of efficiently optimizing the orbitals of generalized valence bond (GVB) wavefunctions are discussed and applied to LiH, BH, H_3, H_(2)O, C_(2)H_6, and O_2. The strong orthogonality and perfect pairing restrictions are tested for the X^(1)Σ^+ state of LiH, the X 1Σ+, a^(3)π, and A^(1)π states of BH, and the H_(2)+D⇄H+HD exchange reaction. The orbitals of H_(2)O and C_(2)H_6 naturally localize into OH, CH, and CC bonding pairs. The nonbonding orbitals of H_(2_O are approximately tetrahedral but this description is only 2 kcal lower than the optimum description in terms of σ and π lone‐pair functions. The calculated rotational barrier for C_(2)H_6 is 3.1 kcal, in good agreement with the experimental value (2.9 kcal). The description of the O2 molecule in the GVB approach is presented and the results of carrying out CI calculations using the GVB orbitals are discussed. The GVB orbitals are found to be a good basis set for configuration interaction calculations. The general features of GVB orbitals in other molecules are summarized.

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Article

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URL	URL Type	Description
http://dx.doi.org/10.1063/1.1678308	DOI	Article
http://link.aip.org/link/doi/10.1063/1.1678308	Publisher	Article

ORCID:

Author	ORCID
Goddard, W. A., III	0000-0003-0097-5716

Additional Information:

© 1972 American Institute of Physics. Received 26 October 1971. We are indebted to Richard Blint, Robert Ladner, and Frank Bobrowicz for their help in the comparisons of the GVB and SOGI methods. We also thank R. Blint for the generous use of his results prior to their publication. Supported in part by a grant (GP-15423) from the National Science Foundation and by a grant (PF-013) from the President's Fund of the California Institute of Technology.

Funders:

Funding Agency	Grant Number
NSF	GP-15423
Caltech President’s Fund	PF-013

Other Numbering System:

Other Numbering System Name	Other Numbering System ID
WAG	0043

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DOI:

10.1063/1.1678308

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CaltechAUTHORS:20120727-105852837

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20120727-105852837

Official Citation:

Self-Consistent Procedures for Generalized Valence Bond Wavefunctions. Applications H[sub 3], BH, H[sub 2]O, C[sub 2]H[sub 6], and O[sub 2] W. J. Hunt, P. J. Hay, and W. A. Goddard III, J. Chem. Phys. 57, 738 (1972), DOI:10.1063/1.1678308

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30 Jul 2012 18:44

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09 Nov 2021 21:29

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