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Picosecond photoisomerization and rotational reorientation dynamics in solution

Lee, M; Bain, AJ; McCarthy, PJ; Han, CH; Haseltine, JN; Smith, AB; Hochstrasser, RM; (1986) Picosecond photoisomerization and rotational reorientation dynamics in solution. The Journal of Chemical Physics , 85 (8) pp. 4341-4347. 10.1063/1.451806. Green open access

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Abstract

The trans-cis isomerization rates for stiff-diphenylbutadiene (S-DPB) in n-alkane solvents were measured using single photon counting methods and the rotational reorientation times τR for S-DPB and trans stilbene were obtained by picosecond polarization spectroscopy. In neither case did τR VS viscosity show Stokes-Einstein-Debye (SED) behavior. The values of τR were used to calculate the angular velocity correlation frequencies β using the Hubbard relation. The variation of isomerization rate with β was found to be predicted well by the Kramers equation when barrier frequencies of 154 cm-1 for stilbene and 16 cm-1 for S-DPB were used. This Kramers-Hubbard fit finesses questions regarding the validity of the one dimensional Kramers model and focuses attention on the SED equation. The dynamical relationship between the torsional friction, important in isomerization, and rotational friction, which determines the overall angular motion of the molecules, is discussed.

Type: Article
Title: Picosecond photoisomerization and rotational reorientation dynamics in solution
Open access status: An open access version is available from UCL Discovery
DOI: 10.1063/1.451806
Publisher version: http://dx.doi.org/10.1063/1.451806
Language: English
Additional information: The following article appeared in: Lee, M; Bain, AJ; McCarthy, PJ; Han, CH; Haseltine, JN; Smith, AB; Hochstrasser, RM; (1986) Picosecond photoisomerization and rotational reorientation dynamics in solution. The Journal of Chemical Physics, 85 (8) pp. 4341-4347, and may be found at: http://dx.doi.org/10.1063/1.451806. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI: https://discovery.ucl.ac.uk/id/eprint/1400110
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