title: Effect of Temperature on the Desorption of Lithium from Molybdenum(110) Surfaces: Implications for Fusion Reactor First Wall Materials.
abstract: Determining the strength of Li binding to Mo is critical to assessing the survivability of Li as a potential first wall material in fusion reactors. We present the results of a joint experimental and theoretical investigation into how Li desorbs from Mo(110) surfaces, based on what can be deduced from temperature-programmed desorption measurements and density functional theory (DFT). Li desorption peaks measured at temperatures ranging from 711 K (1 monolayer, ML) to 1030 K (0.04 ML), with corresponding desorption onsets from 489 to 878 K, follow a trend similar to predicted Gibbs free energies for Li adsorption. Bader charge analysis of DFT densities reveals that repulsive forces between neighboring positively charged Li atoms increase with coverage and thus reduce the bond strength between Mo and Li, thereby lowering the desorption temperature as the coverage increases. Additionally, DFT predicts that Li desorbs at higher temperatures from a surface with vacancies than from a perfect surface, offering an explanation for the anomalously high desorption temperatures for the last Li to desorb from Mo(110). Analysis of simulated local densities of states indicates that the stronger binding to the defective surface is correlated with enhanced interaction between Li and Mo, involving the Li 2s electrons and not only the Mo 4d electrons as in the case of the pristine surface, but also the Mo 5s electrons in the case with surface vacancies. We suggest that steps and kinks present on the Mo(110) surface behave similarly and contribute to the high desorption temperatures. These findings imply that roughened Mo surfaces may strengthen Li film adhesion at higher temperatures.
authors.affiliation: Department of Mechanical and Aerospace Engineering, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Mohan
authors.initials: M
authors.lastname: Chen
authors.affiliation: Department of Chemical and Biological Engineering, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: John
authors.initials: J
authors.lastname: Roszell
authors.affiliation: Department of Chemical and Biological Engineering, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Emanuel V
authors.initials: EV
authors.lastname: Scoullos
authors.affiliation: Department of Mechanical and Aerospace Engineering, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Christoph
authors.initials: C
authors.lastname: Riplinger
authors.affiliation: Department of Chemical and Biological Engineering, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Bruce E
authors.initials: BE
authors.lastname: Koel
authors.affiliation: Department of Mechanical and Aerospace Engineering, Princeton University , Princeton, New Jersey 08544, United States.|Program in Applied and Computational Mathematics and Andlinger Center for Energy and the Environment, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Emily A
authors.initials: EA
authors.lastname: Carter
mesh_terms: D000327:Adsorption; D003198:Computer Simulation; D004583:Electrons; D007554:Isotopes / Q000737:chemistry; D008094:Lithium / Q000737:chemistry*; D008956:Models, Chemical; D008982:Molybdenum / Q000737:chemistry*; D009681:Nuclear Fusion; D009688:Nuclear Reactors; D013499:Surface Properties; D013696:Temperature; D014618:Vacuum
chemical_list: D007554:Isotopes; D008982:Molybdenum; D008094:Lithium