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Diffusional Encounter Rate Constants for Xanthone and 2-Naphthoic Acid by Flash Photolysis Experiments and Brownian Dynamics Simulations - Substantial Effects of Polarizability of the Triplet State.

Diffusional encounter rate constants, for xanthone and 2-naphthoic acid molecules in their triplet states with xanthone or 2-naphthoic acid molecules in their triplet or singlet states, were determined using nanosecond laser flash photolysis spectroscopy. Simultaneously, Brownian dynamics simulations were used to compute these rate constants for assumed models of encountering molecules. Altogether, a global fit to transient absorption progress curves, reporting populations of triplet state xanthone and triplet state 2-naphthoic acid molecules, allowed us to determine six diffusional encounter rate constants from our experiments. The most important result of this study is detection of substantial effects of electric polarizability of molecules in their triplet state, visible for xanthone triplet and 2-naphthoic acid ground states, a homo triplet-triplet annihilation of 2-naphthoic acid and a hetero triplet-triplet annihilation for xanthone and 2-naphthoic acid.