Analysis of the mode-specific excited-state energy distribution and wavelength-dependent photoreaction quantum yield in rhodopsin

Biophys J. 2003 Apr;84(4):2492-501. doi: 10.1016/S0006-3495(03)75054-1.

Abstract

The photoreaction quantum yield of rhodopsin is wavelength dependent: phi(lambda) is reduced by up to 5% at wavelengths to the red of 500 nm but is invariant (phi = 0.65 +/- 0.01) between 450 and 500 nm (Kim et al., 2001). To understand this nonstatistical internal conversion process, these results are compared with predictions of a Landau-Zener model for dynamic curve crossing. The initial distribution of excess photon energy in the 28 Franck-Condon active vibrational modes of rhodopsin is defined by a fully thermalized sum-over-states vibronic calculation. This calculation reveals that absorption by high-frequency unreactive modes (e.g., C[double bond]C stretches) increases as the excitation wavelength is shifted from 570 to 450 nm whereas relatively less energy is deposited into reactive low-frequency modes. This result qualitatively explains the experimentally observed wavelength dependence of phi(lambda) for rhodopsin and reveals the importance of delocalized, torsional modes in the reactive pathway.

Publication types

  • Comparative Study
  • Evaluation Study
  • Research Support, U.S. Gov't, P.H.S.
  • Validation Study

MeSH terms

  • Computer Simulation
  • Dose-Response Relationship, Radiation
  • Energy Transfer*
  • Light
  • Models, Molecular*
  • Rhodopsin / chemistry*
  • Rhodopsin / radiation effects*

Substances

  • Rhodopsin