Theoretical Determination of Rate Constants from Excited States: Application to Benzophenone.

A cost-effective method of theoretically predicting electronic-transition rate constants from the excited states of molecules is reported. This method is based on density functional theory calculations of electronic states and quantitative rate constant determination with the Fermi golden rule. The method is applied to the theoretical determination of the excited-state decay mechanism of photoexcited benzophenone, a representative molecule in photochemistry and biochemistry. Calculated rate constants for benzophenone are quantitatively consistent with experimental ones, which validates the reliability of our rate constant calculation. The calculated population kinetics indicate that S → T → T → S is the predominant decay pathway.