Quantum Chemical Analysis of the Excited State Dynamics of Hydrated Electrons

TL;DR

This study uses quantum calculations to analyze the excited state dynamics of hydrated electrons, revealing insights into ultrafast relaxation processes and transient absorption phenomena in water clusters.

Contribution

It provides a detailed quantum mechanical analysis of hydrated electron excited states, including nonadiabatic relaxation and transient absorption, advancing understanding of electron solvation dynamics.

Findings

50 fs internal conversion dynamics explained

Transient infrared absorptions qualitatively reproduced

Adiabatic relaxation within excited p state identified

Abstract

Quantum calculations are performed for an anion water cluster representing the first hydration shell of the solvated electron in solution. The absorption spectra from the ground state, the instant excited states and the relaxed excited states are calculated including CI-SD interactions. Analytic expressions for the nonadiabatic relaxation are presented. It is shown that the 50fs dynamics recently observed after s->p excitation is best accounted for if it is identified with the internal conversion, preceded by an adiabatic relaxation within the excited p state. In addition, transient absorptions found in the infrared are qualitatively reproduced by these calculations .