The structure of hydrated electron has been studied by mixed quantum/classical (MQC) simulations in the past decades, but there’s still massive controversy in its structure. Previous pseudopotentials (Schnitker et al. 1987; Turi et al. 2001) are generally highly repulsive and give a cavity-like structure where the electron interrupts the hydrogen bonding of the water molecules, ‘digs out’ an empty space and resides in it. Our model (Larsen et al. 2010) however suggests a different picture where wave function of the hydrated electron overlaps with several solvent molecules.  The cavity and non-cavity models, being the results of different pseudopotentials, behave differently in response to a change of temperature. This work gives some definitive experimental predictions that can help distinguish between the two. Resonant Raman Spectra has been calculated with a semi-classical method, where non-cavity model exhibits a strong temperature dependence while the cavity model does not have significant variation with change of temperature. Non-adiabatic dynamics has also been done to study the excited state relaxation of hydrated electron. The non-cavity model shows a fast relaxation from the excited state and slow ground state cooling, while the cavity model gives a slow relaxation and fast cooling. These two mechanisms result in different features in transient absorption spectra that can be experimentally observed.

Mixed quantum and classical simulation of the hydrated electron: Temperature dependence in resonance Raman spectra, excited states relaxation and whether the electron resides in a cavity

251st National Meeting (2016)

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