Should surface science exploit more quantitative experiments?

In recent years two particular methods, scanning probe microscopy and theoretical total energy calculations (based, particularly, on density functional theory), have led to major advances in our understanding of surface science. However, performed to the exclusion of more ‘traditional’ experimental methods that provide quantitative information on the composition, vibrational properties, adsorption and desorption energies, and on the electronic and geometrical structure, the interpretation of the results can be unnecessarily speculative. Combined with these methods, on the other hand, they give considerable added power to the long-learnt lesson of the need to use a range of complementary techniques to unravel the complexities of surface phenomena

The role of reconstruction in self-assembly of alkylthiolate monolayers on coinage metal surfaces

Through a combination of standard laboratory-based surface science methods, together with synchrotron radiation-based normal incidence X-ray standing wave (NIXSW) experiments, the interface structure of simple alkylthiolate ‘self-assembled monolayers’ on Cu(1 1 1), Ag(1 1 1) and Au(1 1 1) has been investigated over the last not, vert, similar15 years. A key conclusion is that in all cases the adsorbate produces a substantial, density-lowering, reconstruction of the outermost metal layer, although the nature of these reconstructions is quite different on the three metals. The main results of these investigations are briefly reviewed and contrasted

Time lower bounds for nonadaptive turnstile streaming algorithms

We say a turnstile streaming algorithm is "non-adaptive" if, during updates, the memory cells written and read depend only on the index being updated and random coins tossed at the beginning of the stream (and not on the memory contents of the algorithm). Memory cells read during queries may be decided upon adaptively. All known turnstile streaming algorithms in the literature are non-adaptive. We prove the first non-trivial update time lower bounds for both randomized and deterministic turnstile streaming algorithms, which hold when the algorithms are non-adaptive. While there has been abundant success in proving space lower bounds, there have been no non-trivial update time lower bounds in the turnstile model. Our lower bounds hold against classically studied problems such as heavy hitters, point query, entropy estimation, and moment estimation. In some cases of deterministic algorithms, our lower bounds nearly match known upper bounds

Water does partially dissociate on the perfect TiO2(110) surface : a quantitative structure determination

There has been a long-standing controversy as to whether water can dissociate on perfect areas of a TiO2(110) surface; most early theoretical work indicated this dissociation was facile, while experiments indicated little or no dissociation. More recently the consensus of most theoretical calculations is that no dissociation occurs. New results presented here, based on analysis of scanned-energy mode photoelectron diffraction data from the OH component of O 1s photoemission, show the coexistence of molecular water and OH species in both atop (OHt) and bridging (OHbr) sites. OHbr can arise from reaction with oxygen vacancy defect sites (Ovac), but OHt have only been predicted to arise from dissociation on the perfect areas of the surface. The relative concentrations of OHt and OHbr sites arising from these two dissociation mechanisms are found to be fully consistent with the initial concentration Ovac sites, while the associated Ti-O bondlengths of the OHt and OHbr species are found to be 1.85±0.08Å and 1.94±0.07 Å, respectively

Bridging the pressure gap : can we get local quantitative structural information at ‘near-ambient’ pressures?

In recent years there have been an increasing number of investigations aimed at ‘bridging the pressure gap’ between UHV surface science experiments on well-characterised single crystal surfaces and the much higher (ambient and above) pressures relevant to practical catalyst applications. By applying existing photon-in/photon-out methods and developing instrumentation to allow photoelectron emission to be measured in higher-pressure sample environments, it has proved possible to obtain surface compositions and spectroscopic fingerprinting of chemical and molecular states of adsorbed species at pressures up to a few millibars. None of these methods, however, provide quantitative structural information on the local adsorption sites of isolated atomic and molecular adsorbate species under these higher-pressure reaction conditions. Methods for gaining this information are reviewed and evaluated

How does your crystal grow? : A commentary on Burton, Cabrera and Frank (1951) 'The growth of crystals and the equilibrium structure of their surfaces'

The key ideas presented in the classic paper ‘The growth of crystals and the equilibrium structure of their surfaces’ by W. K. Burton, N. Cabrera and F. C. Frank, published in Philosophical Transactions A in 1951, are summarized and put in the context of both the state of knowledge at the time of publication and the considerable amount of work since that time that has built on and developed these ideas. Many of these developments exploit the huge increase in the capabilities of computer modelling that complement the original analytic approach of the paper. The dearth of relevant experimental data at the time of the original publication has been transformed by the application of increasingly sophisticated modern methods of surface science. This commentary was written to celebrate the 350th anniversary of the journal Philosophical Transactions of the Royal Society

Effect of surface nanostructure on temperature programmed reaction spectroscopy: First-principles kinetic Monte Carlo simulations of CO oxidation at RuO2(110)

Using the catalytic CO oxidation at RuO2(110) as a showcase, we employ first-principles kinetic Monte Carlo simulations to illustrate the intricate effects on temperature programmed reaction spectroscopy data brought about by the mere correlations between the locations of the active sites at a nanostructured surface. Even in the absence of lateral interactions, this nanostructure alone can cause inhomogeneities that cannot be grasped by prevalent mean-field data analysis procedures, which thus lead to wrong conclusions on the reactivity of the different surface species.Comment: 4 pages including 3 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

The (2√3×3)rect. phase of alkylthiolate self-assembled monolayers on Au(111): a symmetry-constrained structural solution

Low-energy electron-diffraction (LEED) patterns of the Au(111)(2√3×3)rect.-butylthiolate surface phase (a structure also seen in longer alkane chain thiolate self-assembled monolayers) show missing diffracted beams characteristic of glide symmetry, but do not show the larger set of missing beams found in surface x-ray diffraction (SXRD). The difference can be attributed to the greatly enhanced role of multiple scattering in LEED, but the combination of symmetry constraints placed on possible structural models by the observed SXRD and LEED beam extinctions greatly reduces the number of possible structural models. Only three such models are identified, one of which is clearly incompatible with other published experimental data. The relative merits of the remaining models, both involving Au adatom-thiolate moieties, are discussed in the light of the results of previous experimental studies

The local adsorption structure of benzene on Si(001)-(2 × 1): a photoelectron diffraction investigation

Scanned-energy mode C 1s photoelectron diffraction has been used to investigate the local adsorption geometry of benzene on Si(001) at saturation coverage and room temperature. The results show that two different local bonding geometries coexist, namely the 'standard butterfly' (SB) and 'tilted bridge' (TB) forms, with a composition of 58 ± 29% of the SB species. Detailed structural parameter values are presented for both species including Si–C bond lengths. On the basis of published measurements of the rate of conversion of the SB to the TB form on this surface, we estimate that the timescale of our experiment is sufficient for achieving equilibrium, and in this case our results indicate that the difference in the Gibbs free energy of adsorption, ΔG(TB)−ΔG(SB), is in the range −0.023 to +0.049 eV. We suggest, however, that the relative concentration of the two species may also be influenced by a combination of steric effects influencing the kinetics, and a sensitivity of the adsorption energies of the adsorbed SB and TB forms to the nature of the surrounding benzene molecules