360 research outputs found
Spontaneous Water Oxidation at Hematite (α-Fe_2O_3) Crystal Faces
Hematite (α-Fe_2O_3) persists as a promising candidate for photoelectrochemical water splitting, but a slow oxygen evolution reaction (OER) at its surfaces remains a limitation. Here we extend a series of studies that examine pH-dependent surface potentials and electron-transfer properties of effectively perfect low-index crystal faces of hematite in contact with simple electrolyte. Zero-resistance amperometry (ZRA) was performed in a two electrode configuration to quantify spontaneous dark current between hematite crystal face pairs (001)/(012), (001)/(113), and (012)/(113) at pH 3. Exponentially decaying currents initially of up to 200 nA were reported between faces over 4 min experiments. Fourth-order ZRA kinetics indicated rate limitation by the OER for current that flows between (001)/(012) and (001)/(113) face pairs, with the (012) and (113) faces serving as the anodes when paired with (001). The cathodic partner reaction is reductive dissolution of the (001) face, converting surface Fe^(3+) to solubilized aqueous Fe^(2+), at a rate maintained by the OER at the anode. In contrast, OER rate limitation does not manifest for the (012)/(113) pair. The uniqueness of the (001) face is established in terms of a faster intrinsic ability to accept the protons required for the reductive dissolution reaction. OER rate limitation inversely may thus arise from sluggish kinetics of hematite surfaces to dispense with the protons that accompany the four-electron OER. The results are explained in terms of semiquantitative energy band diagrams. The finding may be useful as a consideration for tailoring the design of polycrystalline hematite photoanodes that present multiple terminations to the interface with electrolyte
Molecular structure and free energy landscape for electron transport in the decahaem cytochrome MtrF
Measuring equilibrium properties in aging systems
We corroborate the idea of a close connection between replica symmetry
breaking and aging in the linear response function for a large class of
finite-dimensional systems with short-range interactions. In these system,
characterized by a continuity condition with respect to weak random
perturbations of the Hamiltonian, the ``fluctuation dissipation ratio'' in
off-equilibrium dynamics should be equal to the static cumulative distribution
function of the overlaps. This allows for an experimental measurement of the
equilibrium order parameter function.Comment: 5 pages, LaTeX. The paper has been completely rewritten and shortene
The ecological diversity of vegetation within Urban Parks in the Dabrowski Basin (southern Poland)
The aim of this work is to present the diversity of flora in terms of ecological requirements. The research was
conducted in the area of two urban parks in the area of two cities in southern Poland: Bedzin and Czeladz. These parks were
established in different historical periods, and were planned (and are managed) differently. The results of the investigation
have shown that the occurrence of 192 vascular species has been observed in the Gora Zamkowa (Castle Hill) Park, while in
the Grabek park, 334 such species are known to exist. Such disparity is the result of the occurrence of micro-habitats and of
the differences between the ways the two parks are managed. It is also due to these parks’ different functions. In the first case,
the park area is protected by law. In the latter case, human activity has created a new ecological niche for organisms with a
high degree of ecological tolerance. Based on the ecological values, the following groups of plants were distinguished: saxifrages
grasslands, xerothermic grasslands, beech forests, alder forests and artificial planted trees. Analysis has shown that urban
parks are potential places for growth various type of vegetation and also for increasing biodiversity, and can constitute
particularly important hotspots for biodiversity in the cityscape, even if their primary role is recreational. As the study shows,
the environment of a highly urbanized and industrialized region can also have a positive influence on ecological and floristic
diversity
Frequency dependent specific heat of viscous silica
We apply the Mori-Zwanzig projection operator formalism to obtain an
expression for the frequency dependent specific heat c(z) of a liquid. By using
an exact transformation formula due to Lebowitz et al., we derive a relation
between c(z) and K(t), the autocorrelation function of temperature fluctuations
in the microcanonical ensemble. This connection thus allows to determine c(z)
from computer simulations in equilibrium, i.e. without an external
perturbation. By considering the generalization of K(t) to finite wave-vectors,
we derive an expression to determine the thermal conductivity \lambda from such
simulations. We present the results of extensive computer simulations in which
we use the derived relations to determine c(z) over eight decades in frequency,
as well as \lambda. The system investigated is a simple but realistic model for
amorphous silica. We find that at high frequencies the real part of c(z) has
the value of an ideal gas. c'(\omega) increases quickly at those frequencies
which correspond to the vibrational excitations of the system. At low
temperatures c'(\omega) shows a second step. The frequency at which this step
is observed is comparable to the one at which the \alpha-relaxation peak is
observed in the intermediate scattering function. Also the temperature
dependence of the location of this second step is the same as the one of the
peak, thus showing that these quantities are intimately connected to
each other. From c'(\omega) we estimate the temperature dependence of the
vibrational and configurational part of the specific heat. We find that the
static value of c(z) as well as \lambda are in good agreement with experimental
data.Comment: 27 pages of Latex, 8 figure
Computer Simulations of Supercooled Liquids and Glasses
After a brief introduction to the dynamics of supercooled liquids, we discuss
some of the advantages and drawbacks of computer simulations of such systems.
Subsequently we present the results of computer simulations in which the
dynamics of a fragile glass former, a binary Lennard-Jones system, is compared
to the one of a strong glass former, SiO_2. This comparison gives evidence that
the reason for the different temperature dependence of these two types of glass
formers lies in the transport mechanism for the particles in the vicinity of
T_c, the critical temperature of mode-coupling theory. Whereas the one of the
fragile glass former is described very well by the ideal version of
mode-coupling theory, the one for the strong glass former is dominated by
activated processes. In the last part of the article we review some simulations
of glass formers in which the dynamics below the glass transition temperature
was investigated. We show that such simulations might help to establish a
connection between systems with self generated disorder (e.g. structural
glasses) and quenched disorder (e.g. spin glasses).Comment: 37 pages of Latex, 11 figures, to appear as a Topical Review article
in J. Phys.: Condens. Matte
Physics–Dynamics Coupling in weather, climate and Earth system models: Challenges and recent progress
This is the final version. Available from American Meteorological Society via the DOI in this record.Numerical weather, climate, or Earth system models involve the coupling of components. At a broad level, these components can be classified as the resolved fluid dynamics, unresolved fluid dynamical aspects (i.e., those represented by physical parameterizations such as subgrid-scale mixing), and nonfluid dynamical aspects such as radiation and microphysical processes. Typically, each component is developed, at least initially, independently. Once development is mature, the components are coupled to deliver a model of the required complexity. The implementation of the coupling can have a significant impact on the model. As the error associated with each component decreases, the errors introduced by the coupling will eventually dominate. Hence, any improvement in one of the components is unlikely to improve the performance of the overall system. The challenges associated with combining the components to create a coherent model are here termed physics–dynamics coupling. The issue goes beyond the coupling between the parameterizations and the resolved fluid dynamics. This paper highlights recent progress and some of the current challenges. It focuses on three objectives: to illustrate the phenomenology of the coupling problem with references to examples in the literature, to show how the problem can be analyzed, and to create awareness of the issue across the disciplines and specializations. The topics addressed are different ways of advancing full models in time, approaches to understanding the role of the coupling and evaluation of approaches, coupling ocean and atmosphere models, thermodynamic compatibility between model components, and emerging issues such as those that arise as model resolutions increase and/or models use variable resolutions.Natural Environment Research Council (NERC)National Science FoundationDepartment of Energy Office of Biological and Environmental ResearchPacific Northwest National Laboratory (PNNL)DOE Office of Scienc
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