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The photoisomerization reaction of the retinal chromophore in rhodopsin wascomputationally studied using a two-state two-mode model coupled to thermalbaths. Reaction quantum yields at the steady state (10 ps and beyond) werefound to be considerably different than their transient values, suggesting aweak correlation between transient and steady-state dynamics in these systems.Significantly, the steady-state quantum yield was highly sensitive to minutechanges in system parameters, while transient dynamics was nearly unaffected.Correlation of such sensitivity with standard level spacing statistics of thenonadiabatic vibronic system suggests a possible origin in quantum chaos. Thefeasibility of experimental observation of this phenomenon and its implicationsin condensed-phase photochemistry and biological light sensing are discussed.

Extreme Parametric Sensitivity in the Steady-State Photoisomerization of Model Retinal