First-Principles Dynamics of Fluorine Adsorption on Clean and Monohydrogenated Si{001}

[Image: see text] The interaction of highly reactive species with solid surfaces can result in modes of adsorption quite distinct from the classic molecular and dissociative events that are usually thought to dominate. For instance, compelling experimental evidence suggests that adsorption of F(2) at the Si{001} surface is often initiated by abstraction (and binding at the surface) of just one fluorine atom from the molecule; the second fluorine atom subsequently experiences either a separate atomic adsorption event or ejection from the surface altogether. Molecular dynamics simulations using empirical potentials support this concept but massively overestimate the prevalence of atomic ejection. In this work, we report first-principles molecular dynamics calculations that correctly show atomic ejection to be rare while providing insight into the details of abstractive adsorption. In addition, we also examine the case of F(2) adsorption onto a monohydrogenated Si{001} surface, finding evidence for a different type of abstractive adsorption, in which a hydrogen atom may be removed from the surface to form a short-lived HFF intermediate. The latter rapidly decomposes to produce either HF or (via reaction with another surface hydrogen atom) H(2).