Download PDF by Lewis G.N., Mayer J.E.: A Disproof of the Radiation Theory of Chemical Activation

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By Lewis G.N., Mayer J.E.

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The charges qi were found in a gas-phase CC2 computation for the isolated CyC , whereas q0 D 1. The so computed PMF is indeed a poor approximation. 34). The result of this drawback appears as a large error in the depth of the PMF minimum (ca 10 kcal/mol) Fig. 6 PMF profiles for the TCCI along the Ox axis. Reprinted from Ref. [56] with kind permission of © The American Institute of Physics (2011) 2 The Distribution of Internal Distances for Ionic Pairs in Solvents. . , the true profile B in Fig.

6, where three gas-phase PMF profiles drawn along the Ox axis are shown. Profile A was found by means of a high-level quantum-chemical computation (CC2 [60]). It is considered as a benchmark for other more simplistic approaches. 34) with indices “i ” labeling atomic sites of the cation CyC and index “0” belonging to the iodine anion. Partial electrostatic charges qi , q0 , the interatomic distances Ri 0 , and the corresponding LJ coefficients C12 and C6 are involved in this primitive computation.

Basilevsky et al. , ions without interaction) approximation. R/ and ın (the cluster graph techniques) are formulated [26–28]. 26 reveal and verify the important conclusion that in the infinite dilution limit c ! R/ and exp . R/=kT /, as accepted in Sects. 4, is legitimate. A comment is required regarding the Helmholtz free energy A, which has appeared here instead of the Gibbs free energy G, as used conventionally in other places of this chapter (see Sect. 2). 26). 26) and for its counterpart defined via Eqs.

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A Disproof of the Radiation Theory of Chemical Activation by Lewis G.N., Mayer J.E.


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