Reactive islands as essential mediators of unimolecular conformational isomerization: A dynamical study of 3-phospholene

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Abstract
In this paper we focus on the detailed nonlinear classical dynamics of conformational isomerization. In particular we concentrate on systems which admit phase space structures we call ‘‘reactive islands.’’ Our calculations are on a two degree of freedom model of the molecule 3-phospholene with an experimentally fit potential energy surface by Harthcock and Laane. The reactive islands (RIS) are embedded within and are part of chaotic regions of phase space. We find that the RIS are constructed from a linear stability analysis of the period 1 orbit at the transition state or approximated by a similar analysis on reactive periodic orbits. The two approaches converge as the order of the reactive periodic orbit increases. It is found that the fully constructed RIS have well defined regions of reactivity and thus mediate the process of conformational isomerization.The overlap areas of the RIS give important kinetic information such as probabilities for trapped to reactive motion, reactive to trapped motion, and primary back reaction. The implications of this work lie in precisely identifying the microscopic dynamical pathway for isomerization. The results of this work and its relation to the related work of Gray and Rice as well as its relation to contemporary work in modern dynamics is also discussed.