Kinetics of catalytic OH dissociation on metal surfaces

TY - JOUR

T1 - Kinetics of catalytic OH dissociation on metal surfaces

AU - German, Ernst D.

AU - Sheintuch, Moshe

PY - 2012/3/8

Y1 - 2012/3/8

N2 - A tunnel mechanism of OH dissociation reaction on metal surfaces is suggested and analyzed. Expressions for the rate constant and the activation energy are obtained by calculating the transition probability on semiempirical potential energy surfaces in the framework of the nonadiabatic perturbation theory. The analysis of the transition probability leads to a linear Brønsted-Evans-Polanyi (BEP) relationship between the activation energies and the surface reaction energies (ΔI), correlated by E a = 0.73ΔI + 18 (kcal/mol). This relationship is compared with published literature data. The effect of the electron coupling on the pre-exponential factor is discussed, and the kinetic isotope effect of hydrogen for the reaction is predicted.

AB - A tunnel mechanism of OH dissociation reaction on metal surfaces is suggested and analyzed. Expressions for the rate constant and the activation energy are obtained by calculating the transition probability on semiempirical potential energy surfaces in the framework of the nonadiabatic perturbation theory. The analysis of the transition probability leads to a linear Brønsted-Evans-Polanyi (BEP) relationship between the activation energies and the surface reaction energies (ΔI), correlated by E a = 0.73ΔI + 18 (kcal/mol). This relationship is compared with published literature data. The effect of the electron coupling on the pre-exponential factor is discussed, and the kinetic isotope effect of hydrogen for the reaction is predicted.

UR - http://www.scopus.com/inward/record.url?scp=84858136683&partnerID=8YFLogxK

U2 - 10.1021/jp2106499

DO - 10.1021/jp2106499

M3 - 文章

AN - SCOPUS:84858136683

SN - 1932-7447

VL - 116

SP - 5700

EP - 5709

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 9

ER -