Predicting the kinetics of the dissociative adsorption of homonuclear molecules on metal surfaces in gas phase and solution: I. Rate constant of the elementary step of adiabatic reaction

TY - JOUR

T1 - Predicting the kinetics of the dissociative adsorption of homonuclear molecules on metal surfaces in gas phase and solution

T2 - I. Rate constant of the elementary step of adiabatic reaction

AU - German, Ernst D.

AU - Kuznetsov, Alexander M.

AU - Sheintuch, Moshe

N1 - Funding Information: E.D.G. is partially supported by the Center for Absorption in Science, Ministry of Immigrant Absorption, State of Israel, and A.M.K. gratefully acknowledges partial financial support from the Russian Foundation for Basic Research (grant no. 03-03-32935).

PY - 2004/4/10

Y1 - 2004/4/10

N2 - A model is presented to describe the kinetics of the dissociative adsorption of homonuclear molecules X2 on a metal catalyst in the gas phase and a solvent. The following reaction coordinates are used to construct crossing diabatic potential energy surfaces (PES): the distance y between the X fragments of X2 molecule, the distance x of the X 2 reactant from the surface, the set of coordinates describing possible structural reorganization of the metal surface under adsorption, and the set of coordinates characterizing the state of the solvent polarization if the adsorption proceeds on the metal/solvent interface and is accompanied by a charge transfer. The adiabatic PES is determined by a standard procedure taking into account the resonance splitting 2V of the crossing diabatic surfaces. The activation energy is calculated beyond Condon approximation with due account of the dependence of the splitting 2V on the coordinates x and y. The vibration frequencies of the system at the transition configuration (needed to calculate the pre-exponential factor of the rate constant) are calculated by expanding in a series the adiabatic potential energy at the saddle point on this potential surface. Application of the general equations to a system characterized by specific form of the interactions potentials is given. In the following paper our approach is applied to the dissociative adsorption of oxygen on a Pd(111) surface.

AB - A model is presented to describe the kinetics of the dissociative adsorption of homonuclear molecules X2 on a metal catalyst in the gas phase and a solvent. The following reaction coordinates are used to construct crossing diabatic potential energy surfaces (PES): the distance y between the X fragments of X2 molecule, the distance x of the X 2 reactant from the surface, the set of coordinates describing possible structural reorganization of the metal surface under adsorption, and the set of coordinates characterizing the state of the solvent polarization if the adsorption proceeds on the metal/solvent interface and is accompanied by a charge transfer. The adiabatic PES is determined by a standard procedure taking into account the resonance splitting 2V of the crossing diabatic surfaces. The activation energy is calculated beyond Condon approximation with due account of the dependence of the splitting 2V on the coordinates x and y. The vibration frequencies of the system at the transition configuration (needed to calculate the pre-exponential factor of the rate constant) are calculated by expanding in a series the adiabatic potential energy at the saddle point on this potential surface. Application of the general equations to a system characterized by specific form of the interactions potentials is given. In the following paper our approach is applied to the dissociative adsorption of oxygen on a Pd(111) surface.

KW - Chemisorption

KW - Metallic surfaces

KW - Models of surface kinetics

KW - Surface energy

UR - http://www.scopus.com/inward/record.url?scp=1842506023&partnerID=8YFLogxK

U2 - 10.1016/j.susc.2004.01.033

DO - 10.1016/j.susc.2004.01.033

M3 - 文章

AN - SCOPUS:1842506023

SN - 0039-6028

VL - 554

SP - 159

EP - 169

JO - Surface Science

JF - Surface Science

IS - 2-3

ER -