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The effect of magnetism on hydrogen adsorption and subsurface diffusion through face-centred cubic (fcc) γ-Fe(0 0 1) was investigated using spin-polarised density functional theory (s-DFT). The non-magnetic (NM), ferromagnetic (FM), and antiferromagnetic single (AFM1) and double layer (AFMD) structures were considered. For each magnetic state, the hydrogen preferentially adsorbs at the fourfold site, with adsorption energies of 4.07, 4.12, 4.03 and 4.05 eV/H atom for the NM, FM, AFM1 and AFMD structures. A total barrier of 1.34, 0.90, 1.32 and 1.25 eV and a bulk-like diffusion barrier of 0.6, 0.2, 0.4 and 0.3 eV were calculated for the NM, FM, AFM1 and AFMD magnetic states. The Fe atoms nearest to the H atom exhibited a reduced magnetic moment, whereas the next-nearest neighbour Fe atoms exhibited a non-negligible local perturbation in the magnetic moment. The presence of magnetically ordered structures has a minimal influence on the minimum energy path for H diffusion through the lattice and on the adsorption of H atoms on the Fe(0 0 1) surface, but we computed a significant reduction of the bulk-like diffusion barriers with respect to the non-magnetic state of fcc γ-Fe.

Nitric oxide adsorption on a Au(100) single crystal has been investigated to identify the type of adsorption, the adsorption site, and the orientation and alignment of the adsorbed NO relative to the surface. This was done using a combination of 3D-surface velocity map imaging, near-ambient pressure X-ray photoelectron spectroscopy, and density functional theory. NO was observed to be molecularly adsorbed on gold at ∼200 K. Very narrow angular distributions and cold rotational distributions of photodesorbed NO indicate that NO adsorbs on high-symmetry sites on the Au crystal, with the N-O bond axis close to the surface normal. Our density functional theory calculations show that NO preferentially adsorbs on the symmetric bridge (2f) site, which ensures efficient overlap of the NO π* orbital with the orbitals on the two neighbouring Au atoms, and with the N-O bond axis aligned along the surface normal, in agreement with our conclusions from the rotational state distributions. The combination of XPS, which reveals the orientation of NO on gold, with 3D-surface velocity map imaging and density functional theory thus allowed us to determine the adsorption site, orientation and alignment of nitric oxide adsorbed on Au(100).

This study is concerned with the early stages of hydrogen embrittlement on an atomistic scale. We employed density functional theory to investigate hydrogen diffusion through the (100), (110) and (111) surfaces of γ-Fe. The preferred adsorption sites and respective energies for hydrogen adsorption were established for each plane, as well as a minimum energy pathway for diffusion. The H atoms adsorb on the (100), (110) and (111) surfaces with energies of ∼4.06 eV, ∼3.92 eV and ∼4.05 eV, respectively. The barriers for bulk-like diffusion for the (100), (110) and (111) surfaces are ∼0.6 eV, ∼0.5 eV and ∼0.7 eV, respectively. We compared these calculated barriers with previously obtained experimental data in an Arrhenius plot, which indicates good agreement between experimentally measured and theoretically predicted activation energies. Texturing austenitic steels such that the (111) surfaces of grains are preferentially exposed at the cleavage planes may be a possibility to reduce hydrogen embrittlement.

The adsorption of O atoms on the Fe(1 1 0) surface has been investigated by density functional theory for increasing degrees of oxygen coverage from 0.25 to 1 monolayer, to follow the evolution of the Osingle bondFe(1 1 0) system into an FeO(1 1 1)-like monolayer. We found that the quasi-threefold site is the most stable adsorption site for all coverages, with adsorption energies of ∼2.8–4.0 eV per O atom. Oxygen adsorption results in surface geometrical changes such as interlayer relaxation and buckling, the latter of which decreases with coverage. The calculated vibrational frequencies range from 265 to 470 cm−1 for the frustrated translational modes and 480–620 cm−1 for the stretching mode, and hence are in good agreement with the experimental values reported for bulk FeO wüstite. The hybridization of the oxygen 2p and iron 3d orbitals increases with oxygen coverage, and the partial density of states for the Osingle bondFe(1 1 0) system at full coverage resembles the one reported in the literature for bulk FeO. These results at full oxygen coverage point to the incipient formation of an FeO(1 1 1)-like monolayer that would eventually lead to the bulk FeO oxide layer.

We have computed adsorption energies, vibrational frequencies, surface relaxation and buckling for hydrogen adsorbed on a body-centred-cubic Fe(110) surface as a function of the degree of H coverage. This adsorption system is important in a variety of technological processes such as the hydrogen embrittlement in ferritic steels, which motivated this work, and the Haber–Bosch process. We employed spin-polarised density functional theory to optimise geometries of a six-layer Fe slab, followed by frozen mode finite displacement phonon calculations to compute Fe–H vibrational frequencies. We have found that the quasi-threefold (3f) site is the most stable adsorption site, with adsorption energies of ∼3.0 eV/H for all coverages studied. The long-bridge (lb) site, which is close in energy to the 3f site, is actually a transition state leading to the stable 3f site. The calculated harmonic vibrational frequencies collectively span from 730 to 1220 cm−1, for a range of coverages. The increased first-to-second layer spacing in the presence of adsorbed hydrogen, and the pronounced buckling observed in the Fe surface layer, may facilitate the diffusion of hydrogen atoms into the bulk, and therefore impact the early stages of hydrogen embrittlement in steels.

We measured the fully resolved 3-dimensional velocity distributions of nitric oxide photodesorbed from a gold single crystal. These experiments combine time-of-flight measurements and the velocity map imaging technique to yield velocity distributions resolved in three dimensions for a prototypical surface-adsorbate system. Nitric oxide adsorbed on Au(100) was photodesorbed using a 355 nm laser beam. The desorbed NO molecules were ionised in the gas-phase by resonance-enhanced multi-photon ionisation within a set of velocity map imaging optics. The NO molecules preferentially leave the surface along the surface normal with a very narrow angular distribution, indicating a non-thermal desorption process.