DOI: 10.1063/1.1725051. Pariser—Parr Theory: Quantum Mechanical Integrals from the Benzene Spectrum

Pariser—Parr Theory: Quantum Mechanical Integrals from the Benzene Spectrum

10.1063/1.1725051

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The integrals which occur in Pariser—Parr ASMO—CI theory for carbon atoms at short internuclear distances (≤2.40 Å) can be derived from the spectrum of benzene [R. Pariser, J. Chem. Phys. 24, 250 (1956)]. Previously, various workers have uniformly neglected the highest singly excited configuration in the configuration interaction on the grounds of its high energy and because its inclusion destroys the simple linear formulas for the state energies of benzene. The effect of inclusion of this configuration on the spectral matching method of determining nearest-neighbor βpq, γpq, and γpp, employing the 1B2u, 1B1u, 1E1u, and 3B1u states of benzene has been investigated. The major effect was lowering of [11 | 11] to a value near that expected theoretically when correlation effects are considered. The influence of the new parameters on spectral calculations was explored for benzene, cis- and trans-butadiene, naphthalene, and azulene, and the major effect observed was in the energies of excited triplets. It is suggested that this set of parameters, derived consistently and solely from electronic spectra, will be useful for spectral calculations.

Bibliography

Simmons, H. E. (1964). PariserâParr Theory: Quantum Mechanical Integrals from the Benzene Spectrum. The Journal of Chemical Physics, 40(12), 3554â3562.

Authors 1

Howard E. Simmons (first)

References 42 Referenced 27

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Dates

Type	When
Created	20 years, 7 months ago (Jan. 5, 2005, 11:03 p.m.)
Deposited	1 year, 6 months ago (Feb. 8, 2024, 5:41 p.m.)
Indexed	1 month, 4 weeks ago (July 2, 2025, 12:35 p.m.)
Issued	61 years, 2 months ago (June 15, 1964)
Published	61 years, 2 months ago (June 15, 1964)
Published Print	61 years, 2 months ago (June 15, 1964)

Funders 0

None

BibTeX

@article{Simmons_1964, title={Pariser—Parr Theory: Quantum Mechanical Integrals from the Benzene Spectrum}, volume={40}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1725051}, DOI={10.1063/1.1725051}, number={12}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Simmons, Howard E.}, year={1964}, month=jun, pages={3554–3562} }

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