Advances in Chemical Physics, Vol. 74 - download pdf or read online

By Ilya Prigogine, Stuart A. Rice

ISBN-10: 047161212X

ISBN-13: 9780471612124

This necessary sequence is dedicated to supporting the reader receive normal information regarding a wide selection of issues in chemical physics, which box the editors interpret very generally. Their rationale is to have specialists current complete analyses of matters of curiosity and to inspire the expression of person issues of view.

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Extra resources for Advances in Chemical Physics, Vol. 74

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In the isolated molecule, this “nonadiabatic” coupling leads to phenomena such as internal conversion, where an excited electronic state is coupled to a highly excited isoenergetic vibronic state belonging to a lower electronic state with a large energy gap. The rates of internal conversion are relatively low for the low-lying electronic states (of the order of a nanosecond) and may be neglected in the investigation of crystal states, for which typical evolution times are much shorter. However, in the crystal the electronic states of the excitonic bands have very small separations compared to the isolatedmolecule levels.

C. Influence of the Extended Molecular Electronic Clouds It is clear that the point-dipole lattice model should be abandoned for real crystals where the size of the interacting molecules may become comparable to the intermolecular distances, especially for highly excited m*electronic states. Historically, various nondipolar contributions have been successively considered to obtain reasonable agreement with experimental’’ data. The most important effect has been found to be mixing of molecular states by the crystal field, strongly perturbing the dipolar interactions of weak or moderate transitions.

Assuming only bimolecular interactions, for processes on a single particle, with p # m, n and m # n, we obtain the following terms illustrated diagrammatically: and for processes involving two particles m #n, we have the following diagrams: Here D and M denote the exciton energy stabilization and its transfer amplitude respectively; A and p are analogs for the vibration, and D(') and M(') for the vibron. P and Q are vibron-two-particle-state interactions accompanied, respectively, by exciton and vibration transfer; D(2) and K are SURFACE A N D BULK SPECTROSCOPY OF A MOLECULAR CRYSTAL 55 respectively the two-particle-state energy stabilization and the amplitude of two-particle-state transfer.

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Advances in Chemical Physics, Vol. 74 by Ilya Prigogine, Stuart A. Rice

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