281 research outputs found

### Ab initio statistical mechanics of surface adsorption and desorption: I. H$_2$O on MgO (001) at low coverage

We present a general computational scheme based on molecular dynamics (m.d.)
simulation for calculating the chemical potential of adsorbed molecules in
thermal equilibrium on the surface of a material. The scheme is based on the
calculation of the mean force in m.d. simulations in which the height of a
chosen molecule above the surface is constrained, and subsequent integration of
the mean force to obtain the potential of mean force and hence the chemical
potential. The scheme is valid at any coverage and temperature, so that in
principle it allows the calculation of the chemical potential as a function of
coverage and temperature. It avoids all statistical mechanical approximations,
except for the use of classical statistical mechanics for the nuclei, and
assumes nothing in advance about the adsorption sites. From the chemical
potential, the absolute desorption rate of the molecules can be computed,
provided the equilibration rate on the surface is faster than the desorption
rate. We apply the theory by {\em ab initio} m.d. simulation to the case of
H$_2$O on MgO (001) in the low-coverage limit, using the Perdew-Burke-Ernzerhof
(PBE) form of exchange-correlation. The calculations yield an {\em ab initio}
value of the Polanyi-Wigner frequency prefactor, which is more than two orders
of magnitude greater than the value of $10^{13}$ s$^{-1}$ often assumed in the
past. Provisional comparison with experiment suggests that the PBE adsorption
energy may be too low, but the extension of the calculations to higher
coverages is needed before firm conclusions can be drawn. The possibility of
including quantum nuclear effects by using path-integral simulations is noted.Comment: 11 pages + 10 figure

### First-principles kinetic Monte Carlo simulations for heterogeneous catalysis, applied to the CO oxidation at RuO2(110)

We describe a first-principles statistical mechanics approach enabling us to
simulate the steady-state situation of heterogeneous catalysis. In a first step
density-functional theory together with transition-state theory is employed to
obtain the energetics of all relevant elementary processes. Subsequently the
statistical mechanics problem is solved by the kinetic Monte Carlo method,
which fully accounts for the correlations, fluctuations, and spatial
distributions of the chemicals at the surface of the catalyst under
steady-state conditions. Applying this approach to the catalytic oxidation of
CO at RuO2(110), we determine the surface atomic structure and composition in
reactive environments ranging from ultra-high vacuum (UHV) to technologically
relevant conditions, i.e. up to pressures of several atmospheres and elevated
temperatures. We also compute the CO2 formation rates (turnover frequencies).
The results are in quantitative agreement with all existing experimental data.
We find that the high catalytic activity of this system is intimately connected
with a disordered, dynamic surface ``phase'' with significant compositional
fluctuations. In this active state the catalytic function results from a
self-regulating interplay of several elementary processes.Comment: 18 pages including 9 figures; related publications can be found at
http://www.fhi-berlin.mpg.de/th/th.htm

### The sticking probability of D2O-water on ice: Isotope effects and the influence of vibrational excitation

International audienceThe present study measures the sticking probability of heavy water (D2O) on H2O- and on D2O-ice and probes the influence of selective OD-stretch excitation on D2O sticking on these ices. Molecular beam techniques are combined with infrared laser excitation to allow for precise control of incident angle, translational energy, and vibrational state of the incident molecules. For a translational energy of 69 kJ/mol and large incident angles (θ ≥ 45°), the sticking probability of D2O on H2O-ice was found to be 1% lower than on D2O-ice. OD-stretch excitation by IR laser pumping of the incident D2O molecules produces no detectable change of the D2O sticking probability (<10−3). The results are compared with other gas/surface systems for which the effect of vibrational excitation on trapping has been probed experimentally

### Ad- and desorption of Rb atoms on a gold nanofilm measured by surface plasmon polaritons

Hybrid quantum systems made of cold atoms near nanostructured surfaces are
expected to open up new opportunities for the construction of quantum sensors
and for quantum information. For the design of such tailored quantum systems
the interaction of alkali atoms with dielectric and metallic surfaces is
crucial and required to be understood in detail. Here, we present real-time
measurements of the adsorption and desorption of Rubidium atoms on gold
nanofilms. Surface plasmon polaritons (SPP) are excited at the gold surface and
detected in a phase sensitive way. From the temporal change of the SPP phase
the Rubidium coverage of the gold film is deduced with a sensitivity of better
than 0.3 % of a monolayer. By comparing the experimental data with a Langmuir
type adsorption model we obtain the thermal desorption rate and the sticking
probability. In addition, also laser-induced desorption is observed and
quantified.Comment: 9 pages, 6 figure

### Structure, stability, and mobility of small Pd clusters on the stoichiometric and defective TiO$_2$ (110) surfaces

We report on the structure and adsorption properties of Pd$_n$ ($n=1-4$)
clusters supported on the rutile TiO$_2$ (110) surfaces with the possible
presence of a surface oxygen vacancy or a subsurface Ti-interstitial atom. As
predicted by the density functional theory, small Pd clusters prefer to bind to
the stoichiometric titania surface or at sites near subsurface Ti-interstitial
atoms. The adsorption of Pd clusters changes the electronic structure of the
underlying surface. For the surface with an oxygen vacancy, the charge
localization and ferromagnetic spin states are found to be largely attenuated
owing to the adsorption of Pd clusters. The potential energy surfaces of the Pd
monomer on different types of surfaces are also reported. The process of
sintering is then simulated via the Metropolis Monte Carlo method. The presence
of oxygen vacancy likely leads to the dissociation of Pd clusters. On the
stoichiometric surface or surface with Ti-interstitial atom, the Pd monomers
tend to sinter into larger clusters, whereas the Pd dimer, trimer and tetramer
appear to be relatively stable below 600 K. This result agrees with the
standard sintering model of transition metal clusters and experimental
observations.Comment: 27 pages, 11 figure

### On the statistical mechanics of prion diseases

We simulate a two-dimensional, lattice based, protein-level statistical
mechanical model for prion diseases (e.g., Mad Cow disease) with concommitant
prion protein misfolding and aggregation. Our simulations lead us to the
hypothesis that the observed broad incubation time distribution in
epidemiological data reflect fluctuation dominated growth seeded by a few
nanometer scale aggregates, while much narrower incubation time distributions
for innoculated lab animals arise from statistical self averaging. We model
`species barriers' to prion infection and assess a related treatment protocol.Comment: 5 Pages, 3 eps figures (submitted to Physical Review Letters

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