title: Excitation of biomolecules with incoherent light: quantum yield for the photoisomerization of model retinal.
abstract: Cis-trans isomerization in retinal, the first step in vision, is often computationally studied from a time-dependent viewpoint. Motivation for such studies lies in coherent pulsed laser experiments that explore the isomerization dynamics. However, such biological processes take place naturally in the presence of incoherent light, which is expected to excite a nonevolving mixture of stationary states. Here the isomerization problem is considered from the latter viewpoint and applied to a standard two-state, two-mode linear vibronic coupling model of retinal that explicitly includes a conical intersection between the ground and first excited electronic states. The calculated quantum yield at 500 nm agrees well with both the previous time-dependent calculations of Hahn and Stock (0.63) [ J. Phys. Chem. B 2000, 104, 1146-1149 ] and with experiment (0.65 ± 0.01), as does its wavelength dependence. Significantly, the effects of environmental relaxation on the quantum yield in this well-established model are found to be negligible. The results make clear the connection of the photoisomerization quantum yield to properties of stationary eigenstates, providing alternate insights into conditions for yield optimization.
authors.affiliation: Chemical Physics Theory Group, Department of Chemistry, and Center for Quantum Information and Quantum Control, University of Toronto , Toronto, Ontario M5S 3H6, Canada.
authors.forename: T V
authors.initials: TV
authors.lastname: Tscherbul
authors.forename: P
authors.initials: P
authors.lastname: Brumer
mesh_terms: D008027:Light; D008958:Models, Molecular; D015394:Molecular Structure; D055668:Photochemical Processes; D011789:Quantum Theory; D012172:Retinaldehyde / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D012172:Retinaldehyde