DOI: 10.1063/1.437217. A theoretical analysis of the two-photon properties of linear polyenes and the visual chromophores

A theoretical analysis of the two-photon properties of linear polyenes and the visual chromophores

10.1063/1.437217

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A self-consistent field molecular orbital formalism for calculating molecular two-photon absorptivities is presented based on the combined use of the Pariser–Parr–Pople π-electron method including full single and double excitation configuration interaction and Monson and McClain’s two-photon orientational averaging procedures. The formalism is applied to a series of linear, nonlinear, and retinyl polyenes to study the effect of chain length, conformation, and polarity on the calculated two-photon absorptivities for various photon polarization and propagation relationships. The calculations indicate that the low-lying ’’1Ag*−’’ covalent state should be strongly two-photon allowed in virtually all polyenes, whether polar, nonpolar, linear, or nonlinear, provided a strongly one-photon allowed ’’1Bu*+’’ state is nearby. The two-photon absorptivity of the ’’1Ag*−’’ state for two linearly polarized photons is predicted to increase with increasing polyene chain length. Linearly polarized light produces the strongest two-photon absorption for polyenes with four or more conjugated double bonds. The two-photon absorptivity and polarization ratio of the ’’1Bu*−’’ state is predicted to be proportional to the degree of nonlinearity introduced into the polyene chain as a result of cis linkages. Accordingly, this state is responsible for the ’’cis band’’ in two-photon spectroscopy.

Bibliography

Birge, R. R., & Pierce, B. M. (1979). A theoretical analysis of the two-photon properties of linear polyenes and the visual chromophores. The Journal of Chemical Physics, 70(1), 165â178.

Authors 2

Robert R. Birge (first)
Brian M. Pierce (additional)

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Dates

Type	When
Created	22 years, 6 months ago (Feb. 27, 2003, 5:52 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 2:11 p.m.)
Indexed	2 days, 1 hour ago (Sept. 4, 2025, 9:30 a.m.)
Issued	46 years, 8 months ago (Jan. 1, 1979)
Published	46 years, 8 months ago (Jan. 1, 1979)
Published Print	46 years, 8 months ago (Jan. 1, 1979)

Funders 0

None

BibTeX

@article{Birge_1979, title={A theoretical analysis of the two-photon properties of linear polyenes and the visual chromophores}, volume={70}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.437217}, DOI={10.1063/1.437217}, number={1}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Birge, Robert R. and Pierce, Brian M.}, year={1979}, month=jan, pages={165–178} }

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