Primary events in the bacteriorhodopsin photocycle Torsional vibrational dephasing in the first excited electronic state》.pdf

Chemical Physics 313 (2005) 51–62 /locate/chemphys Primary events in the bacteriorhodopsin photocycle: Torsional vibrational dephasing in the first excited electronic state Andrew C. Terentis 1, Laszlo Ujj 2, Halina Abramczyk 3, George H. Atkinson * Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA Received 8 October 2004; accepted 20 December 2004 Available online 20 January 2005 Abstract A new model of the primary events of the bacteriorhodopsin (BR) photocycle is derived from the analysis of vibrational spec- troscopic data obtained from native BR (BR-570) and three artificial BR pigments containing structurally modified retinals with carbon rings bridging specific C–C and C@C bonds (BR6.11, BR6.9, and BR5.12). Vibrational spectra from the ground-states and from picosecond intermediates appearing in the respective photo-reactions are measured by coherent anti-Stokes Raman spec- troscopy (CARS). Special attention is given to an analysis of the time-dependent bandwidth changes in vibrational bands assigned to the C@C stretching and hydrogen-out-of-plane (HOOP) modes. The bandwidth analysis reveals an intramolecular, vibrational dephasing mechanism in the lowest-energy electronic excited state, involving a coupling between out-of-plane motion along the ret- inal backbone and C@C stretching modes. The mode-selective coupling plays a significant role as a precursor to the all-trans ! 13- cis isomerization in BR and accounts for primary events in the BR photocycle not previously demonstrated. 2004 Elsevier B.V. All rights reserved. Keywords: Bacteriorhodopsin; Dephasing; CARS; Photocyc