Energy Dissipation into the Solvent during Proton Transfer Occurs via Acoustic Phonons.

Abstract

In photochemistry, rapid energy dissipation into the solvent is mandatory to prevent radiation damages. By optical pump THz spectroscopy, we are able to follow the details of the energy dissipation mechanism upon photoexcitation of the photoacid to the hydrogen-bonded network of water: Based on the frequency maps subsequent to photoexcitation, we propose that energy transfer takes place via propagation of an acoustic phonon. The dissipation into the solvent can be rationalized by an initial first hydration shell response followed by energy dissipation via an acoustic phonon. Surprisingly, for the first 10 ps, the propagation in the water network can be described by a wave packet with a constant group velocity, indicating a long-range correlation. After 300 ps, thermalization in the liquid jet is reached and the THz spectrum reflects a Boltzmann population, corresponding a temperature increase of ΔT = 0.5 °C.