Breakdowns of linear-response are exhibited in numerous chemical processes. It has been shown that the Gaussian statistics approximation has a close connection to linear response, but exhibits key distinctions that make the approximation more generally applicable. Unfortunately, there are still systems in which the Gaussian statistics approximation is disobeyed. The “dipole-flip” model, for example, exhibits deviations from the Gaussian statistics assumption—the statistics of the energy gap are Gaussian, but are nonstationary. This model has been investigated further with an emphasis on potential nonstationary effects from higher order terms in the Gaussian statistics approximation. These effects possibly serve as a check for the validity of linear-response-type approximations for other nonlinear dynamical processes. These nonlinear effects are also investigated in the dynamics of charged push-pull polyenes, which can be modeled as a dipole in solution.

On the breakdown of linear response theory: An investigation of Gaussian statistics and the dipole flip model

251st National Meeting (2016)

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