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

By Ilya Prigogine, Stuart A. Rice

This necessary sequence is dedicated to aiding the reader receive basic information regarding a large choice of themes in chemical physics, which box the editors interpret very greatly. Their reason is to have specialists current entire analyses of topics of curiosity and to motivate the expression of person issues of view.

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This approximation is well adapted to the intramolecular vibrations and, to a less degree, to the libration modes, particularly to optical modes. 15), when the frequency change upon excitation is neglected. 15). This approximation amounts to considering only the R , dependence of the local energy Dnm. We find that the xs do not depend on q. 30) The B(b) are operators of excitons (vibrations); the Vnmare intermolecular interactions; t, a dimensionless parameter, characterizes the linear coupling.

37b) - (cf. Appendix C). 40) we obtain the ground state with E’j = 0, and the excited state with i t E = 1, with its new frequency a,, and with a shift of the fundamental vibration, due in part to the change of the zero-point energy (hR,/2 - hf2,/2) and in part to the Franck-Condon shift giving the energy stabilization - E F C . )-”28’”16) represents the state 1:’) when BtB = 0, and the state 1:) when BtB = 1. 38) as combinations of the renormalized excitation operators. b. T h e Vibronic Exciton.

A brief discussion of the method of Ewald allows us to distinguish, in the dipolar sums, the dispersion due to short-range forces (coulombic interactions between neighboring molecules) and the nonanalytic dispersion due to longrange forces originating both from long-range coulombic interactions and from retarded interactions. The structure at K = 0 of the elementary excitations, depending on the direction of the wave vector (nonanalyticity), is thus shown to be the signature of the infinite range of the dipole-dipole interactions.

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