DOI: 10.1063/1.457697. Photoisomerization of diphenylbutadiene in low-viscosity nonpolar solvents: Experimental manifestations of multidimensional Kramers behavior and cluster effects

Photoisomerization of diphenylbutadiene in low-viscosity nonpolar solvents: Experimental manifestations of multidimensional Kramers behavior and cluster effects

10.1063/1.457697

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The photoisomerization of diphenylbutadiene was studied by picosecond absorption spectroscopy over wide pressure and temperature ranges in liquid and supercritical alkanes, CO2, SF6, and He. The reaction shows typical features of a thermal unimolecular reaction on the S1 potential energy surface. The rate can be expressed by a combination of standard unimolecular rate theory and Kramers–Smoluchowski theory. However, multidimensional behavior manifests itself in the transition to the gas phase low pressure range as well as to the high density Kramers–Smoluchowski range: in the former case, the low pressure limit of a unimolecular reaction of the polyatomic molecule is approached; in the latter case, the effective imaginary barrier frequency shows a marked apparent temperature dependence. The experiments also suggest contributions of reactant–solvent cluster interactions, which modify the barrier height even in nonpolar solvents.

Bibliography

Gehrke, Ch., Schroeder, J., Schwarzer, D., Troe, J., & VoÃ, F. (1990). Photoisomerization of diphenylbutadiene in low-viscosity nonpolar solvents: Experimental manifestations of multidimensional Kramers behavior and cluster effects. The Journal of Chemical Physics, 92(8), 4805â4816.

Authors 5

Ch. Gehrke (first)
J. Schroeder (additional)
D. Schwarzer (additional)
J. Troe (additional)
F. Voß (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:12 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 6:23 a.m.)
Indexed	1 month, 3 weeks ago (July 2, 2025, 1:51 p.m.)
Issued	35 years, 4 months ago (April 15, 1990)
Published	35 years, 4 months ago (April 15, 1990)
Published Print	35 years, 4 months ago (April 15, 1990)

Funders 0

None

BibTeX

@article{Gehrke_1990, title={Photoisomerization of diphenylbutadiene in low-viscosity nonpolar solvents: Experimental manifestations of multidimensional Kramers behavior and cluster effects}, volume={92}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.457697}, DOI={10.1063/1.457697}, number={8}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Gehrke, Ch. and Schroeder, J. and Schwarzer, D. and Troe, J. and Voß, F.}, year={1990}, month=apr, pages={4805–4816} }

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