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Solvent Polarity Effects on CIS-Stilbene Photochemistry from the First Femtoseconds to the Final Products

  • Conference paper
Reaction Dynamics in Clusters and Condensed Phases

Part of the book series: The Jerusalem Symposia on Quantum Chemistry and Biochemistry ((JSQC,volume 26))

Abstract

The ultrafast torsional isomerization and ring closure reactions of photoexcited cis-stilbene have been examined in hexane, cyclohexane, methanol, and acetonitrile solvents through a combination of ground state resonance Raman intensities, two-color uv picosecond anti-Stokes resonance Raman scattering, and product quantum yield measurements. The quantum yields for ring closure to ground state dihydrophenanthrene are factors of two to three higher in the nonpolar solvents than in the polar ones, while the yield of trans-stilbene is slightly higher in the polar solvents. Vibrationally hot ground-state trans-stilbene is formed within the 10 ps time resolution of the time-resolved Raman experiments in both solvents, but the subsequent vibrational cooling is about a factor of two faster in methanol than in cyclohexane. The resonance Raman spectra of the cis-stilbene ground state exhibit slightly greater relative intensities in modes involving primarily out-of-plane and/or hydrogen wagging or rocking motions in the polar solvents than in the hydrocarbons. These observations, together with the femtosecond transient absorption and fluorescence data from other groups, indicate that increasing solvent polarity causes vertically excited cis-stilbene to distort more rapidly along the torsional isomerization coordinate, shortening the excited state lifetime and decreasing the quantum yield for the competing ring closure reaction.

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Authors and Affiliations

  1. Department of Chemistry, University of Rochester, Rochester, NY, 14627-0216, USA

    Anne B. Myers & Jon-Marc Rodier

  2. Department of Chemistry, University of Hong Kong, Pokfulam Road, Hong Kong, China

    David L. Phillips

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Editors and Affiliations

  1. The Israel Academy of Sciences and Humanities, Jerusalem, Israel

    J. Jortner

  2. The Fritz Haber Center for Molecular Dynamics, The Hebrew University of Jerusalem, Jerusalem, Israel

    R. D. Levine

  3. Institut de Biologie Physico-Chimique (Fondation Edmond de Rothschild), Paris, France

    B. Pullman

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Myers, A.B., Rodier, JM., Phillips, D.L. (1994). Solvent Polarity Effects on CIS-Stilbene Photochemistry from the First Femtoseconds to the Final Products. In: Jortner, J., Levine, R.D., Pullman, B. (eds) Reaction Dynamics in Clusters and Condensed Phases. The Jerusalem Symposia on Quantum Chemistry and Biochemistry, vol 26. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0786-0_19

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  • DOI: https://doi.org/10.1007/978-94-011-0786-0_19

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