Photoisomerisation of trans-stilbene in solution may be directly assisted by solvent collisions

Details Photoisomerisation of trans-stilbene in solution may be directly assisted by solvent collisions Photoisomerisation of trans-stilbene in solution may be directly assisted by solvent collisions

2012-04-10

arxiv.org/abs/1204.2142v1

Physics

Chemical Physics

8 pages, 4 figures

Scientific paper

Gas phase thermal isomerization rates of trans-stilbene obey the Arrhenius law at T~300 K, indicating that intramolecular vibrational redistribution (IVR) is complete or not restrictive for the reaction. In solution the rates increase ten-fold and become nearly independent on intramolecular temperature (or excitation wavelength). These observations are difficult to express through RRKM theory. Mechanisms suggested so far, like restricted IVR, nonadiabaticity, or solvent-dependent barriers, may explain only the increase in the rates but not the wavelength independence. We propose that solute-solvent collisions directly promote isomerization, in addition to intramolecular activation. The two activation mechanisms can be experimentally distinguished by the weak dependence on excitation wavelength.

Affiliated with

Also associated with

No associations

Rating

Photoisomerisation of trans-stilbene in solution may be directly assisted by solvent collisions does not yet have a rating. At this time, there are no reviews or comments for this scientific paper.

If you have personal experience with Photoisomerisation of trans-stilbene in solution may be directly assisted by solvent collisions, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Photoisomerisation of trans-stilbene in solution may be directly assisted by solvent collisions will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFWR-SCP-O-645288