We explore the role of solvent effects on the dynamics on a two-dimensional model potential exhibiting a post-transition state valley ridge inflection (VRI) point. The solvent is modelled as a <i>finite</i> collection of bilinearly coupled harmonic oscillators in order to understand the influence of finite size effects of the solvent cage on product selectivity. The effect of various parameterizations of the bath, including coupling strength and directionality of the system/bath coupling, are shown to influence both the intrinsic reaction coordinate and the dynamics of the reaction. The mechanism of energy exchange between the system and the bath is examined in the short-time dynamics and in a time/frequency analysis. Low frequency bath modes are shown to play an important role in solvent caging effects. Recurrences of energy in the model degrees of freedom at long times and other limitations of the model are discussed. Solvent influence on product selectivity is compared to previous studies on the model system in the absence of a finite harmonic bath.

Solvent effects in the dynamics on potentials with post-transition state valley ridge inflection points

253rd National Meeting (2017)

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