First-Principles Theory of Surface Thermodynamics and Kinetics

In this Letter, with the aim to improve upon this approach, we combine state-of-the-art procedures of (i) microscopic theories, i.e., DFT electronic structure calculations and (ii) macroscopic phenomenological approaches, i.e., lattice gas and rate equations, and Monte Carlo schemes. On doing this, we present a consistent first-principles-based approach for calculation of the thermodynamic and kinetic properties of an adsorbate, such as heats of adsorption, temperature programmed desorption (TPD) spectra, and the surface phase diagram. We have chosen the system of oxygen at Ru(0001) for which detailed structural [4 ‐9], thermodynamic [10], and kinetic data [11,12] exist. We will show that, with the present approach, a realistic description of these physical properties is indeed feasible.