Displacive surface phases formed by hydrogen chemisorption on W {001}

A detailed LEED study is reported of the surface phases stabilised by hydrogen chemisorption on W {001}, over the temperature range 170 to 400 K, correlated with absolute determinations of surface coverages and sticking probabilities. The saturation coverage at 300 K is 19(± 3) × 10¹⁴ atoms cm^?2, corresponding to a surface stoichiometry of WH₂, and the initial sticking probability for both H₂ and D₂ is 0.60 ± 0.03, independent of substrate temperature down to 170 K. Over the range 170 to 300 K six coverage-dependent temperature-independent phases are identified, and the transition coverages determined. As with the clean surface $\text{(}\text{2}\text{×}\text{2}\text{)R45°}$ displacive phase, the c(2 × 2)-H phase is inhibited by the presence of steps and impurities over large distances (～20 Å), again strongly indicative of CDW-PLD mechanisms for the formation of the H-stabilised phases. These phases are significantly more temperature stable than the clean $\text{(}\text{2}\text{×}\text{2}\text{)R45°}$, the most stable being a c(2 × 2)-H split half-order phase which is formed at domain stoichiometries between WH_0.3 and WH_0.5. LEED symmetry analysis, the dependence of half-order intensity and half-width on coverage, and I-V spectra indicate that the c(2 × 2)-H phase is a different displacive structure from that determined by Debe and King for the clean $\text{(}\text{2}\text{×}\text{2}\text{)R45°}$. LEED I-V spectra are consistent with an expansion of the surface-bulk interlayer spacing from 1.48 to 1.51 Å as the hydrogen coverage increases to ～4 × 10¹⁴ atoms cm^?2. The transition from the split half-order to a streaked half-order phase is found to be correlated with changes in a range of other physical properties previously reported for this system. As the surface stoichiometry increases from WH to WH₂ a gradual transition occurs between a phase devoid of long-range order to well-ordered (1 × 1)-H. Displacive structures are proposed for the various phases formed, based on the hypothesis that at any coverage the most stable phase is determined by the gain in stability produced by a combination of chemical bonding to form a local surface complex and electron-phonon coupling to produce a periodic lattice distortion. The sequence of commensurate, incommensurate and disordered structures are consistent with the wealth of data now available for this system. Finally, a simple structural model is suggested for the peak-splitting observed in desorption spectra.