Intramolecular Energy Relaxation and Statistical Rate Theory

概要

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Statistical rate theory is essentially based on the state counting without any restrictions other than the energy and the angular momentum conservation. In this work, two kinds of restrictions are introduced into the statistical theory. The first restriction is related to the intramolecular energy flow within the reacting molecular system. The excess energy of reaction is made distributed with some bias favoring a specific degree of freedom. That is, the statistical weight of each product state is not equal but biased. The biased product energy distribution observed in various reactions can be well reproduced by using an appropriate form of restriction. The product energy distributions in F+H_2→HF+H and H+F_2→HF+F are treated under such category. In the second restriction, the components of the angular momentum vector of the reaction products are biased so as to express a specific vectorial relation between the departing products and the initial parent system. The vector correlation observed in many photofragment experiments suggests a proper vectorial restriction which can reproduce fragment energy distributions. The photofragmentation of the NO dimer which is known to occur within the molecular plane offers such an example. The energy state distribution of the NO fragments is well reproduced only when the vectorial restrictions are taken into account.
理論物理学刊行会の論文
1994-08-12