Tunneling chemical kinetics

QUANTUM MECHANICAL TUNNELING CHEMICAL KINETICS HYDROGEN TUNNELING KINETIC ISOTOPE EFFECTS QUANTUM REQUIREMENT QUANTUM YIELD QUANTUM YIELD FLUQRESCENCE ACTINOMETER Quasi-axial,... 

K.I. Zamaraev, R.F. Khairutdinov and V.P. Zhdanov, The Comprehensive Chemical Kinetics, Vol. 30 Long-Range Electron Tunnelling in Chemistry (North-Holland, Amsterdam, 1989). 

Compton, R. G. Comprehensive Chemical Kinetics Electron Tunneling in Chemistry-, 1989, Vol. 30. 

Zamaraev KI, Khairutdinov RF, Zhdanov VP (1989) Electron tunneling in chemistry. Comprehensive chemical kinetics (Ed Compton RG) vol 30. Elsevier, Amsterdam... 

Refs. [i] Conway BE (1999) Electrochemical processes involving H adsorbed at metal electrode surfaces. In Wieckowski A (ed) Interfacial electrochemistry, theory, experiment, and applications. Marcel Dekker, New York, pp 131-150 [ii] Climent V, Gomez R, Orts JM, Rodes A, AldazA, Feliu JM (1999) Electrochemistry, spectroscopy, and scanning tunneling microscopy images of small single-crystal electrodes. In Wieckowski A (ed) Interfacial electrochemistry, theory, experiment, and applications. MarcelDekker, New York, pp 463-475 [Hi] Calvo E] (1986) Fundamentals. The basics of electrode reactions. In Bamford CH, Compton RG (eds) Comprehensive chemical kinetics, vol. 26. Elsevier, Amsterdam, pp 1-78... 

The concept of tunneling in chemical kinetics was initiated by Hund [2] in discussing the problem of delocalization of electron between two potential wells. It was stated for the first time in this work that for a double-well potential with typical vibration frequency at in the wells and barrier height V , the tunneling transfer probability decreases exponentially with growing 2V jh(o, and therefore, for typical values of of 0.2-2 eV and fico =0.1 eV, it... 

The rest of the paper is organized as follows The second chapter gives an introduction into the theoretical description of tunneling phenomena and chemical kinetics. After a short summary about the connection of symmetry and tunneling, the basic properties of coherent and incoherent rotational tunneling and their relation to NMR spectroscopy are discussed and the empiric Bell [77] tunnel model is introduced, which is a powerful semi-empirical tool for the description of chemical kinetics in the transition from the coherent to the incoherent regime. 

The Harwell code CFX has been described already in the section on dispersion models. The chemical kinetics submodel specifies a chemical system of several species and reactions with an offered selection of different combustion models. Heat tr sfer is accounted for by convection, conduction, and radiation [1]. Examples calculated at the Research Center Julich include Russian RUT tests and combustion experiments conducted in a Swiss railroad tunnel. 

The discussion in this section is supposed to elucidate the important problem of the role of nuclear tunneling in chemical kinetics. As mentioned in the introduction, there exist in the literature large discrepancies and contradictions between the various definitions... 

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