Read e-book online Advances in Chemical Physics, Vol. 68 PDF

By Ilya Prigogine

ISBN-10: 0471849014

ISBN-13: 9780471849018

A part of a sequence dedicated to aiding the reader receive common information regarding a large choice of issues in chemical physics. Its objective is to give finished analyses of matters of curiosity and to inspire the expression of person issues of view.

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Extra info for Advances in Chemical Physics, Vol. 68

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The position of the second band (the main fluorescence in polar solvents at higher temperatures) is strongly polarity dependent, testifying of its charge-transfer character. 75 The horizontal portion for weak polarities reflects the solvent insensitivity of the FB band dominating in this range. We have thus two fluorescing states, one with zero and the other with a very high dipole moment. 4 Fig. 14. Anomalous Stokes red shift A;= - GF versus solvent polarity Af' = - 1)/(2s + 1) - (n' - 1 ) / 2 ( 2 n 2 + 1) of different 22 neat solvents as numbered in Ref.

11). The thickness Ar, is of minor importance since it will not appear explicitly in our final results. The surface S will be divided rather arbitrarily in subsurfaces S, of subgroups i for each atom except hydrogen, that is, for C, 0, and N in our examples, which carry the fractional charge Q j of the subgroup i. Only five sizes S j = k,(4 - li) are allowed for each subgroup surface according to the number 1; of bonds to another subgroup center nuclei j , so that 4 - l j counts the sum of the number of bonds to H atoms, of 2p,-orbitals for double bonds, and of lone-pair orbitals of the ith central atom.

From the slopes, the formal activation energies E , and E, for B*+A* and reverse reaction, respectively, can be derived. thus due to the energetic stabilization of the A* state, the larger part results from the energy destabilization of the twisted ground state owing to combined effects of ground-state intramolecular rotational barrier and intermolecular solute-solvent interactions directly after photon emission. The polarity of the solvent strongly affects both the shapes of the excited state and of the ground-state surfaces: For increasing solvent polarity, the A* state is more strongly stabilized than the B* state, resulting in a deformation of the excited state potential ( E , - E, increases).

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Advances in Chemical Physics, Vol. 68 by Ilya Prigogine


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