DOI: 10.1063/1.446786. <i>Ab initio</i> determination of bond length dependence of the correlated valence shell Hamiltonian of CH: Comparison with semiempirical theories

Ab initio determination of bond length dependence of the correlated valence shell Hamiltonian of CH: Comparison with semiempirical theories

10.1063/1.446786

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The exact ab initio effective valence shell Hamiltonian , which is mimicked by semiempirical theories of valence, is calculated for CH at 11 bond lengths using quasidegenerate many-body perturbation theory to incorporate extensive correlation contributions. Least squares fits of the bond length dependence of the calculated CH matrix elements provide simple formulas which are compared with the intuitive forms introduced into semiempirical theories. Some of the semiempirical formulas, e.g., one-center, one-electron integrals and two-center, two-electron integrals, are in good agreement with our correlated ab initio calculations, while others display substantial departures. For example, the bond length dependence of one-center, two-electron integrals, which are assumed to be independent of bond length in semiempirical theories, is substantial but physically understandable. Corrections are found to the assumed proportionality of resonance and overlap integrals. The bond length dependence of nonclassical three-electron integrals is presented along with the hybrid and exchange integrals that are ignored in zero differential overlap methods.

Bibliography

Sun, H., & Freed, K. F. (1984). Ab initio determination of bond length dependence of the correlated valence shell Hamiltonian of CH: Comparison with semiempirical theories. The Journal of Chemical Physics, 80(2), 779â788.

Authors 2

Hosung Sun (first)
Karl F. Freed (additional)

References 47 Referenced 21

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Dates

Type	When
Created	22 years, 6 months ago (Feb. 28, 2003, 12:18 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 8:45 p.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 9:59 a.m.)
Issued	41 years, 7 months ago (Jan. 15, 1984)
Published	41 years, 7 months ago (Jan. 15, 1984)
Published Print	41 years, 7 months ago (Jan. 15, 1984)

Funders 0

None

BibTeX

@article{Sun_1984, title={Ab initio determination of bond length dependence of the correlated valence shell Hamiltonian of CH: Comparison with semiempirical theories}, volume={80}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.446786}, DOI={10.1063/1.446786}, number={2}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Sun, Hosung and Freed, Karl F.}, year={1984}, month=jan, pages={779–788} }

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