Implementation of new TPD analysis techniques in the evaluation of second order desorption kinetics of cyanogen from Cu(001)

The interactions of cyanide species with a copper (001) surface were studied with temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Adsorbed cyanide species (CN(a)) undergo recombinative desorption evolving molecular cyanogen (C(2)N(2)). As the adsorbed CN species charge upon adsorption, mutually repulsive dipolar interactions lead to a marked desorption energy reduction with increasing CN(a) coverages. Two new TPD analysis approaches were developed, which used only accurately discernible observables and which do not assume constant desorption energies, E(d), and pre-exponential values, ν. These two approaches demonstrated a linear variation of E(d) with instantaneous coverage. The first approach involved an analysis of the variations of desorption peak asymmetry with initial CN coverages. The second quantitative approach utilized only temperatures and intensities of TPD peaks, together with deduced surface coverages at the peak maxima, also as a function of initial surface coverages. Parameters derived from the latter approach were utilized as initial inputs for a comprehensive curve fit analysis technique. Excellent fits for all experimental desorption curves were produced in simulations. The curve fit analysis confirms that the activation energy of desorption of 170-180 kJ/mol at low coverage decreases by up to 14-15 kJ/mol at CN saturation.