647 research outputs found
Interplay between adsorbates and polarons: CO on rutile TiO(110)
Polaron formation plays a major role in determining the structural,
electrical and chemical properties of ionic crystals. Using a combination of
first principles calculations and scanning tunneling microscpoy/atomic force
microscopy (STM/AFM), we analyze the interaction of polarons with CO molecules
adsorbed on the rutile TiO(110) surface. Adsorbed CO shows attractive
coupling with polarons in the surface layer, and repulsive interaction with
polarons in the subsurface layer. As a result, CO adsorption depends on the
reduction state of the sample. For slightly reduced surfaces, many adsorption
configurations with comparable adsorption energies exist and polarons reside in
the subsurface layer. At strongly reduced surfaces, two adsorption
configurations dominante: either inside an oxygen vacancy, or at surface
Ti sites, coupled with a surface polaron
Formation and dynamics of small polarons on the rutile TiO(110) surface
Charge trapping and formation of polarons is a pervasive phenomenon in
transition metal oxide compounds, in particular at the surface, affecting
fundamental physical properties and functionalities of the hosting materials.
Here we investigate via first-principle techniques the formation and dynamics
of small polarons on the reduced surface of titanium dioxide, an archetypal
system for polarons, for a wide range of oxygen vacancy concentrations. We
report how the essential features of polarons can be adequately accounted in
terms of few quantities: the local structural and chemical environment, the
attractive interaction between negatively charged polarons and positively
charged oxygen vacancies, and the spin-dependent polaron-polaron Coulomb
repulsion. We combined molecular dynamics simulations on realistic samples
derived from experimental observations with simplified static models, aiming to
disentangle the various variables at play. We find that depending on the
specific trapping site, different types of polarons can be formed, with
distinct orbital symmetries and different degree of localization and structural
distortion. The energetically most stable polaron site is the subsurface Ti
atom below the undercoordinated surface Ti atom, owing to a small energy cost
to distort the lattice and a suitable electrostatic potential. Polaron-polaron
repulsion and polaron-vacancy attraction determine the spatial distribution of
polarons as well as the energy of the polaronic in-gap state. In the range of
experimentally reachable oxygen vacancy concentrations the calculated data are
in excellent agreement with observations, thus validating the overall
interpretation
Direct assessment of the proton affinity of individual surface hydroxyls with non-contact atomic force microscopy
The state of protonation/deprotonation of surfaces has far-ranging
implications in all areas of chemistry: from acid-base catalysis and the
electro- and photocatalytic splitting of water, to the behavior of
minerals and biochemistry. The acidity of a molecule or a surface site
is described by its proton affinity (PA) and pK value (the
negative logarithm of the equilibrium constant of the proton transfer reaction
in solution). For solids, in contrast to molecules, the acidity of individual
sites is difficult to assess. For mineral surfaces such as oxides they are
estimated by semi-empirical concepts such as bond-order valence sums, and
also increasingly modeled with first-principles molecular dynamics
simulations. Currently such predictions cannot be tested - the
experimental measures used for comparison are typically average quantities
integrated over the whole surface or, in some cases, individual crystal
facets, such as the point of zero charge (pzc). Here we assess
individual hydroxyls on InO(111), a model oxide with four different
types of surface oxygen atoms, and probe the strength of their hydrogen bond
with the tip of a non-contact atomic force microscope (AFM). The force curves
are in quantitative agreement with density-functional theory (DFT)
calculations. By relating the results to known proton affinities and
pK values of gas-phase molecules, we provide a direct measure of
proton affinity distributions at the atomic scale
Course Allocation via Stable Matching
The allocation of students to courses is a wide-spread and repeated task in higher education, often accomplished by a simple first-come first-served (FCFS) procedure. FCFS is neither stable nor strategy-proof, however. The Nobel Prize in Economic Sciences was awarded to Al Roth and Lloyd Shapley for theirwork on the theory of stable allocations. This theory was influential in many areas, but found surprisingly little application in course allocation as of yet. In this paper, different approaches for course allocation with a focus on appropriate stablematchingmechanisms are surveyed. Two such mechanisms are discussed in more detail, the Gale- Shapley student optimal stable mechanism (SOSM) and the efficiency adjusted deferred acceptance mechanism (EADAM). EADAM can be seen as a fundamental recent contribution which recovers efficiency losses from SOSM at the expense of strategy-proofness. In addition to these two important mechanisms, a survey of recent extensions with respect to the assignment of schedules of courses rather than individual courses is provided. The survey of the theoretical literature is complemented with results of a field experiment, which help understand the benefits of stable matching mechanisms in course allocation applications
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