THE KINETICS OF OVERCOMING THE “ENTROPY BARRIER”статья
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Дата последнего поиска статьи во внешних источниках: 3 мая 2017 г.
Аннотация:The escape of a point particle from a cavity of an arbitrary configuration through a small orifice in a cavity wall is considered as a model of entropy barrier overcoming. The dynamics of the particle is determined by collisions with the wall and the dissipative action of the medium. As in reactions with overcoming energy barriers (the Kramers theory), three characteristic regimes can be identified depending on the intensity of friction: diffusion
and intermediate regimes and the region of weak friction. For all of them, analytic dependences of rate constants on problem parameters were obtained. The procedure for sewing solutions together, similar to that employed in the Kramers theory, gives a unified equation for the transmission factor over the whole range of friction values. In the weak friction mode, overcoming the entropy barrier generally leads to a nonexponential kinetics.