Bicycle-pedal isomerization in a rhodopsin chromophore model

J Am Chem Soc. 2009 Jan 14;131(1):16-7. doi: 10.1021/ja805586z.

Abstract

Probing the isomerization of a retinal chromophore model we have found the first ab initio realization of the so-called "bicycle-pedal mechanism". In an ensemble of 47 starting geometries generated by ground-state zero-point-energy sampling one single trajectory followed the aforementioned reaction mode which was proposed by Warshel in 1976. Furthermore restrained optimization of synchronous rotation mode shows that two-double-bond isomerization is barrierless for the conrotatory and disrotatory pathway.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Computer Simulation
  • Isomerism
  • Models, Molecular
  • Polyenes / chemistry*
  • Retinaldehyde / chemistry
  • Schiff Bases / chemistry
  • Sensory Rhodopsins / chemistry*
  • Thermodynamics

Substances

  • Polyenes
  • Schiff Bases
  • Sensory Rhodopsins
  • Retinaldehyde