Proton force field treatment

Force Field Treatment of Proton and Hydrogen Transfer in Molecular Systems... 

Calculations using conventional TST and the Bigeleisen-Wolfsberg [16] treatment for isotope effects have demonstrated that thd = 1-44 is a useful benchmark for primary hydrogen isotope effects. Using empirical harmonic force fields and various reactant-state and transition-state geometries, More O Ferrall and Kouba [30] found, for proton-transfer models, that the exponents were within 2% of the 1.44 value, and similar computational approaches gave Xhd = 1.43-1.45 (343 K)... 

Bruckner et al. have further developed the double Fourier expansion treatment of unperturbed polypropylene chains of iso-, syndio-, and intermediate tacticities, incorporating vicinal proton coupling-constant data into the analysis by the standard use of straight matrix correlation products for the estimation of rotational angle probabilities. To include non-bonded interactions arising between carbon atoms separated by more than four bonds, the repulsive term of the force field was enhanced to provide an improved interpretation of the experimental data. 

In the second chapter, Appleby presents a detailed discussion and review in modem terms of a central aspect of electrochemistry Electron Transfer Reactions With and Without Ion Transfer. Electron transfer is the most fundamental aspect of most processes at electrode interfaces and is also involved intimately with the homogeneous chemistry of redox reactions in solutions. The subject has experienced controversial discussions of the role of solvational interactions in the processes of electron transfer at electrodes and in solution, especially in relation to the role of Inner-sphere versus Outer-sphere activation effects in the act of electron transfer. The author distils out the essential features of electron transfer processes in a tour de force treatment of all aspects of this important field in terms of models of the solvent (continuum and molecular), and of the activation process in the kinetics of electron transfer reactions, especially with respect to the applicability of the Franck-Condon principle to the time-scales of electron transfer and solvational excitation. Sections specially devoted to hydration of the proton and its heterogeneous transfer, coupled with... 

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