Cluster and barrier effects in the temperature and pressure dependence of the photoisomerization of trans-stilbene

Article abstract of DOI:10.1063/1.459020

The pressure and temperature dependence of the photoisomerization rate coeficient of trans-stilbene in the S₁ state have been measured in the solvents C2H6, C3H8, C4H10, Xe, Co2, SF6, and CHF3.At constant temperature, the pressure dependences up to 6 kbar can be well represented by the Kramers-Smoluchowski model.The comparison of results in different solvents cleary indicates the importance of reactant-solvent cluster formation modifying the height and imaginary frequency of the barrier.The change of the temperature dependence with pressure points towards a multidimensional barrier of nonseparable character.Multidimensional barrier effects manifest themselves most clearly via the temperature dependence of the rate coefficient in the Kramers-Smoluchowski limit.

Full text of DOI:10.1063/1.459020

Cluster and barrier effects in the temperature and pressure dependence of
the photoisomerization of transstilbene
J. Schroeder, D. Schwarzer, J. Troe, and F. Voß
Citation: J. Chem. Phys. 93, 2393 (1990); doi: 10.1063/1.459020
View online: http://dx.doi.org/10.1063/1.459020
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v93/i4
Published by the American Institute of Physics.
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