Hard versus soft dynamics for adsorption-desorption kinetics: Exact results in one-dimension.
The adsorption-desorption kinetics is discussed in the framework of the kinetic lattice-gas model. The master equation formalism has been introduced to describe the evolution of the system, where the transition probabilities are written as an expansion of the occupation configurations of all neighboring sites. Since the detailed balance principle determines half of the coefficients that arise from the expansion, it is necessary to introduce ad hoc, a dynamic scheme to get the rest of them. Three schemes of the so-called hard dynamics, in which the probability of transition from single site cannot be factored into a part which depends only on the interaction energy and one that only depends on the field energy, and five schemes of the so-called soft dynamics, in which this factorization is possible, were introduced for this purpose. It is observed that for the hard dynamic schemes, the equilibrium and nonequilibrium observables, such as adsorption isotherms, sticking coefficients, and thermal desorption spectra, have a normal or physical sustainable behavior. While for the soft dynamics schemes, with the exception of the transition state theory, the equilibrium and nonequilibrium observables have several problems. Some of them can be regarded as abnormal behavior.
Manzi
S J
SJ
Departamento de Física, Instituto de Física Aplicada (INFAP)-CONICET, Universidad Nacional de San Luis, Chacabuco 917, 5700 San Luis, Argentina.
Huespe
V J
VJ
Belardinelli
R E
RE
Pereyra
V D
VD
D000327:Adsorption; D003198:Computer Simulation; D005740:Gases / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D015233:Models, Statistical
D005740:Gases