Kavli Affiliate: David T. Limmer
| First 5 Authors: Aditya N. Singh, David T. Limmer, , ,
| Summary:
The modern theory of rare events is grounded in near equilibrium ideas,
however many systems of modern interest are sufficiently far from equilibrium
that traditional approaches do not apply. Using the recently developed
variational path sampling methodology, we study systems evolving within
nonequilibrium steady states to elucidate how reactive processes are altered
away from equilibrium. Variational path sampling provides access to ensembles
of reactive events, and a means of quantifying the relative importance of each
dynamical degree of freedom in such processes. With it, we have studied the
conformational change of a solute in an active bath. We illustrate how energy
injection generically enhances the rates of rare events, even when energy is
not directed into specific reactive modes. By studying the folding and
unfolding transitions of a grafted polymer under shear, we illustrate how
nonequilibrium reactive processes do not follow gradient paths due to the
emergence of persistent currents. The breaking of detailed balance allows for
the mechanisms of forward and backward reactions to be distinct, enabling novel
pathways to be explored and designed, and states unstable in equilibrium to
become stabilized kinetically away from it. The analysis presented in this work
establishes some basic principles for nonequilibrium reactive events, and is
made possible by the use of a numerical method that does not invoke proximity
to equilibrium or requires strong prior assumptions about the mechanism of
reaction.
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