Journal of Physical Chemistry A, Vol.102, No.10, 1691-1696, 1998
The role of solvent friction in an orbital symmetry controlled reaction : Ring closure of a carbonyl ylide to cis-2,3-diphenyloxirane
The dynamics of the orbital symmetry controlled ring closure of the trans-ylide, formed upon the 266 nm photolysis of trans-2,3-diphenyloxirane, to produce cis-2,3-diphenyloxirane is examined in a variety of n-alkane solvents as a function of temperature. An unsuccessful attempt was made to model the kinetics within the theoretical framework developed by Kramers for a one-dimensional reaction coordinate. A model developed by Grote and Hynes that employs a frequency-dependent friction was found to give a significantly better fit to the experimental data. The possibility that a multidimensional reaction coordinate is necessary to describe the reaction dynamics is discussed.
Keywords:FREQUENCY-DEPENDENT FRICTION;TRANS-STILBENE;PHOTOISOMERIZATION DYNAMICS;PHOTOCHEMICAL ISOMERIZATION;PERICYCLIC-REACTIONS;HYDRODYNAMIC THEORY;NORMAL-ALKANES;BARRIER;REORIENTATION;SIMULATION