Environmental effects on nonlinear optical chromophore performance. Calculation of molecular quadratic hyperpolarizabilities in solvating media

Santo Di Bella, Tobin J Marks, Mark A Ratner

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Abstract

The molecular quadratic hyperpolarizabilities of a wide series of π-conjugated, donor-acceptor chromophores in various solvation media are calculated using the INDO/S (ZINDO) sum over excited particle hole states formalism. The energy terms of the perturbation theory are corrected for solvent effects by means of a continuum Onsager cavity model, based on the reaction field model. Calculated hyperpolarizability values including solvent effects are in excellent agreement with experimental electric field induced second-harmonic generation data taken in solution. The calculations show that red shifts of the lowest energy electronic charge-transfer transition upon solvation are the most important feature altering hyperpolarizability values on passing from the gas phase to solution. A linear correlation found between the hyperpolarizability and the energy of the lowest charge-transfer transition demonstrates the general validity of the simple two-state model in predicting solvation trends in hyperpolarizability for donor-acceptor chromophores. The consistency of this model is probed by calculating chromophore hyperpolarizabilities in different solvents and for different fundamental laser frequencies.

Original languageEnglish
Pages (from-to)4440-4445
Number of pages6
JournalJournal of the American Chemical Society
Volume116
Issue number10
Publication statusPublished - May 18 1994

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Chromophores
Environmental impact
Solvation
Charge transfer
Lasers
Harmonic generation
Gases
Electric fields

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Environmental effects on nonlinear optical chromophore performance. Calculation of molecular quadratic hyperpolarizabilities in solvating media",
abstract = "The molecular quadratic hyperpolarizabilities of a wide series of π-conjugated, donor-acceptor chromophores in various solvation media are calculated using the INDO/S (ZINDO) sum over excited particle hole states formalism. The energy terms of the perturbation theory are corrected for solvent effects by means of a continuum Onsager cavity model, based on the reaction field model. Calculated hyperpolarizability values including solvent effects are in excellent agreement with experimental electric field induced second-harmonic generation data taken in solution. The calculations show that red shifts of the lowest energy electronic charge-transfer transition upon solvation are the most important feature altering hyperpolarizability values on passing from the gas phase to solution. A linear correlation found between the hyperpolarizability and the energy of the lowest charge-transfer transition demonstrates the general validity of the simple two-state model in predicting solvation trends in hyperpolarizability for donor-acceptor chromophores. The consistency of this model is probed by calculating chromophore hyperpolarizabilities in different solvents and for different fundamental laser frequencies.",
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T1 - Environmental effects on nonlinear optical chromophore performance. Calculation of molecular quadratic hyperpolarizabilities in solvating media

AU - Di Bella, Santo

AU - Marks, Tobin J

AU - Ratner, Mark A

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N2 - The molecular quadratic hyperpolarizabilities of a wide series of π-conjugated, donor-acceptor chromophores in various solvation media are calculated using the INDO/S (ZINDO) sum over excited particle hole states formalism. The energy terms of the perturbation theory are corrected for solvent effects by means of a continuum Onsager cavity model, based on the reaction field model. Calculated hyperpolarizability values including solvent effects are in excellent agreement with experimental electric field induced second-harmonic generation data taken in solution. The calculations show that red shifts of the lowest energy electronic charge-transfer transition upon solvation are the most important feature altering hyperpolarizability values on passing from the gas phase to solution. A linear correlation found between the hyperpolarizability and the energy of the lowest charge-transfer transition demonstrates the general validity of the simple two-state model in predicting solvation trends in hyperpolarizability for donor-acceptor chromophores. The consistency of this model is probed by calculating chromophore hyperpolarizabilities in different solvents and for different fundamental laser frequencies.

AB - The molecular quadratic hyperpolarizabilities of a wide series of π-conjugated, donor-acceptor chromophores in various solvation media are calculated using the INDO/S (ZINDO) sum over excited particle hole states formalism. The energy terms of the perturbation theory are corrected for solvent effects by means of a continuum Onsager cavity model, based on the reaction field model. Calculated hyperpolarizability values including solvent effects are in excellent agreement with experimental electric field induced second-harmonic generation data taken in solution. The calculations show that red shifts of the lowest energy electronic charge-transfer transition upon solvation are the most important feature altering hyperpolarizability values on passing from the gas phase to solution. A linear correlation found between the hyperpolarizability and the energy of the lowest charge-transfer transition demonstrates the general validity of the simple two-state model in predicting solvation trends in hyperpolarizability for donor-acceptor chromophores. The consistency of this model is probed by calculating chromophore hyperpolarizabilities in different solvents and for different fundamental laser frequencies.

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