Molecular dynamics study of the equilibrium flux of gas molecules to a fractal/rough surface: Effects of gas atom diameter

The frequency of collisions of ideal gas molecules (argon) with a rough surface has been studied. The rough/fractal surface was created using the random deposition technique. By applying various depositions the surface roughness was controlled and, as a measure of irregularity, the fractal dimensions of the surfaces were determined. The surfaces were next immersed in ideal gas and the numbers of collisions with these surfaces were counted. The calculations were carried out using the simplified molecular dynamics simulation technique (only hard core repulsions were assumed). The calculations were performed for various ratios of gas phase atoms diameter to the surface substrate atoms diameter. The results obtained showed that the size of a gas phase atom has crucial influence on the relation between the frequency of collision and the surface fractal dimension     

Kinetic adsorption energy distributions of rough surfaces: a computational study

The adsorption energy distribution usually refers to localized monolayers of adsorbate at thermodynamic equilibrium. Many papers have been published that analyze its influence on adsorption isotherms, heats of adsorption, and adsorption kinetics. However, the adsorption energy distribution, in its classical thermodynamic equilibrium sense, may be not as useful as expected. This is because many important processes involving adsorption have dynamic character and reactant particles have a finite time for penetration of the adsorbent. The above suggests that some adsorption centers located in less accessible fragments of the surface can be invisible in a dynamic process. However, under conditions allowing the thermodynamic equilibrium such adsorption centers could noticeably contribute to the adsorption energy distribution. The aim of this work is to measure the adsorption energy distributions of special rough surfaces using a dynamic method. This method is based on the molecular dynamics simulation of an ideal gas flowing over a sample surface. The ideal gas particles penetrate the surface, and at the moment of collision of a gas particle with the surface the Lennard-Jones potential energy is calculated. This energy can be identified with the adsorption energy at a given point on the surface. The surfaces used in the calculations have been created using two surface growth models (i.e., random deposition and ballistic deposition). The application of these highly disordered surfaces enables us to draw some general conclusions about the properties of real surfaces that are usually far from any deterministic geometry.     

Studies of the collision frequency of ideal gas particles with the surfaces of the objects created using the ballistic deposition technique

This paper is a continuation of our studies of the collision frequency of ideal gas particles with the rough/fractal surfaces. Here, we applied a more realistic surface growth model, i.e. ballistic deposition for creation of fractal objects. We found that the collision frequency with irregular surfaces is the linear function of pressure and this frequency per unit pressure is quite a complicated function of the surface fractal dimension as well as the diameter of colliding particle. The collision frequency with rough surfaces cannot be exactly described by the analytical formula called the Langmuir-Hertz equation. However, we have stated that the deviations of the true collision frequency from the Langmuir-Hertz prediction are not huge and in typical catalytic studies the error introduced by replacing the true frequency by the Langmuir-Hertz prediction can be safely neglected. We have also studied the probability of finding on the surface an atom which has been hit a certain number of times by a gas particle. This probability reveals an interesting behaviour for small gas particles, i.e. it perfectly correlates with the number of directions from which the surface atom is accessible from the gas phase. We have also estimated the evolution of the adsorption energy distribution with the increasing fractal dimension of the surface in the ballistic deposition.