Temperature dependence of the hydrated electron’s excited-state relaxation. I. Simulation predictions of resonance Raman and pump-probe transient absorption spectra of cavity and non-cavity models

We use one-electron non-adiabatic mixed quantum/classical simulations to explore the temperature dependence of both the ground-state structure and the excited-state relaxation dynamics of the hydrated electron. We compare the results for both the traditional cavity picture and a more recent non-cavity model of the hydrated electron and make definite predictions for distinguishing between the different possible structural models in future experiments. We find that the traditional cavity model shows no temperature-dependent change in structure at constant density, leading to a predicted resonance Raman spectrum that is essentially temperature-independent. In contrast, the non-cavity model predicts a blue-shift in the hydrated electron’s resonance Raman O–H stretch with increasing temperature. The lack of a temperature-dependent ground-state structural change of the cavity model also leads to a prediction of little change with temperature of both the excited-state lifetime and hot ground-state cooling time o...