A Dynamical Theory of Electron Transfer: Crossover from Weak to Strong Electronic Coupling

We present a real-time path integral theory for the rate of electron transfer reactions. Using graph theoretic techniques, the dynamics is expressed in a formally exact way as a set of integral equations. With a simple approximation for the self-energy, the rate can then be computed analytically to all orders in the electronic coupling matrix element. We present results for the crossover region between weak (nonadiabatic) and strong (adiabatic) electronic coupling and show that this theory provides a rigorous justification for the salient features of the rate expected within conventional electron transfer theory. Nonetheless, we find distinct characteristics of quantum behavior even in the strongly adiabatic limit where classical rate theory is conventionally thought to be applicable. To our knowledge, this theory is the first systematic dynamical treatment of the full crossover region.Comment: 11 pages, LaTeX, 8 Postscript figures to be published in J. Chem. Phy

Faraday Instability in a Surface-Frozen Liquid

Faraday surface instability measurements of the critical acceleration, a_c, and wavenumber, k_c, for standing surface waves on a tetracosanol (C_24H_50) melt exhibit abrupt changes at T_s=54degC above the bulk freezing temperature. The measured variations of a_c and k_c vs. temperature and driving frequency are accounted for quantitatively by a hydrodynamic model, revealing a change from a free-slip surface flow, generic for a free liquid surface (T>T_s), to a surface-pinned, no-slip flow, characteristic of a flow near a wetted solid wall (T < T_s). The change at T_s is traced to the onset of surface freezing, where the steep velocity gradient in the surface-pinned flow significantly increases the viscous dissipation near the surface.Comment: 4 pages, 3 figures. Physical Review Letters (in press

Quantum Kinetic Theory of Condensate Growth---Comparison of Experiment and Theory

In a major extension of our previous model (C.W. Gardiner, P. Zoller, R.J. Ballagh and M.J. Davis, Phys. Rev. Lett. 79, 1793 (1997)) of condensate growth, we take account of the evolution of the occupations of lower trap levels, and of the full Bose-Einstein formula for the occupations of higher trap levels. We find good agreement with experiment, especially at higher temperatures. We also confirm the picture of the ``kinetic'' region of evolution, introduced by Kagan et al, for the time up to the initiation of the condensate. The behavior after initiation essentially follows our original growth equation, but with a substantially increased rate coefficient W^{+}.Comment: RevTeX, 4 pages and 4 eps figure

Random Sequential Adsorption: From Continuum to Lattice and Pre-Patterned Substrates

The random sequential adsorption (RSA) model has served as a paradigm for diverse phenomena in physical chemistry, as well as in other areas such as biology, ecology, and sociology. In the present work, we survey aspects of the RSA model with emphasis on the approach to and properties of jammed states obtained for large times in continuum deposition versus that on lattice substrates, and on pre-patterned surfaces. The latter model has been of recent interest in the context of efforts to use pre-patterning as a tool to improve selfassembly in micro- and nanoscale surface structure engineering

Condensate growth in trapped Bose gases

We study the dynamics of condensate formation in an inhomogeneous trapped Bose gas with a positive interatomic scattering length. We take into account both the nonequilibrium kinetics of the thermal cloud and the Hartree-Fock mean-field effects in the condensed and the noncondensed parts of the gas. Our growth equations are solved numerically by assuming that the thermal component behaves ergodically and that the condensate, treated within the Thomas-Fermi approximation, grows adiabatically. Our simulations are in good qualitative agreement with experiment, however important discrepancies concerning details of the growth behaviour remain.Comment: 28 pages, 11 figures. Changes made to the introduction, Sec. VI, Sec. VII, and included additional growth curves in Fig. 1

Thermal Properties of Two-Dimensional Advection Dominated Accretion Flow

We study the thermal structure of the widely adopted two-dimensional advection dominated accretion flow (ADAF) of Narayan & Yi (1995a). The critical radius for a given mass accretion rate, outside of which the optically thin hot solutions do not exist in the equatorial plane, agrees with one-dimensional study. However, we find that, even within the critical radius, there always exists a conical region of the flow, around the pole, which cannot maintain the assumed high electron temperature, regardless of the mass accretion rate, in the absence of radiative heating. This could lead to torus-like advection inflow shape since, in general, the ions too will cool down. We also find that Compton preheating is generally important and, if the radiative efficiency, defined as the luminosity output divided by the mass accretion rate times the velocity of light squared, is above sim 4x10^-3, the polar region of the flow is preheated above the virial temperature by Compton heating and it may result in time-dependent behaviour or outflow while accretion continues in the equatorial plane. Thus, under most relevant circumstances, ADAF solutions may be expected to be accompanied by polar outflow winds. While preheating instabilities exist in ADAF, as for spherical flows, the former are to some extent protected by their characteristically higher densities and higher cooling rates, which reduce their susceptibility to Compton driven overheating.Comment: 18 pages including 4 figures. AASTEX. Submitted to Ap

Optimizing Technological Parameters of the Reduction Processes in Treating Steels in a Ladle Furnace

This work reports the possible development of reduction processes when treating the molten metal and slag using a ladle furnace under conditions of intensive stirring with an inert gas. The industrial data have been received, confirming the possibility of decreasing the concentration of ferrous and manganese oxides in the slag and stabilizing the contents of manganese and silicon in the metal

Self-sculpting of a dissolvable body due to gravitational convection

© 2018 American Physical Society. Natural sculpting processes such as erosion or dissolution often yield universal shapes that bear no imprint or memory of the initial conditions. Here we conduct laboratory experiments aimed at assessing the shape dynamics and role of memory for the simple case of a dissolvable boundary immersed in a fluid. Though no external flow is imposed, dissolution and consequent density differences lead to gravitational convective flows that in turn strongly affect local dissolving rates and shape changes, and we identify two distinct behaviors. A flat boundary dissolving from its lower surface tends to retain its overall shape (an example of near perfect memory) while bearing small-scale pits that reflect complex near-body flows. A boundary dissolving from its upper surface tends to erase its initial shape and form an upward spike structure that sharpens indefinitely. We propose an explanation for these different outcomes based on observations of the coupled shape dynamics, concentration fields, and flows

Kinetics of Bose-Condensation

The process of condensation in the system of scalar Bosons with weak $\lambda \phi^4$ interaction is considered. Boltzmann kinetic equation is solved numerically. Bose condensation proceeds in two stages: At the first stage condensate is still absent but there is non-zero inflow of particles towards $\vec{{\bf p}} = 0$ and the distribution function at $\vec{{\bf p}} = 0$ grows from finite values to infinity. At the second stage there are two components, condensate and particles, reaching their equilibrium values. We show that the evolution in both stages proceeds in a self - similar way and find the time needed for condensation, which is finite.Comment: 12 pages, LaTeX RevTeX 3.0, includes 4 eps figure

Diffuse-Charge Dynamics in Electrochemical Systems

The response of a model micro-electrochemical system to a time-dependent applied voltage is analyzed. The article begins with a fresh historical review including electrochemistry, colloidal science, and microfluidics. The model problem consists of a symmetric binary electrolyte between parallel-plate, blocking electrodes which suddenly apply a voltage. Compact Stern layers on the electrodes are also taken into account. The Nernst-Planck-Poisson equations are first linearized and solved by Laplace transforms for small voltages, and numerical solutions are obtained for large voltages. The ``weakly nonlinear'' limit of thin double layers is then analyzed by matched asymptotic expansions in the small parameter $\epsilon = \lambda_D/L$, where $\lambda_D$ is the screening length and $L$ the electrode separation. At leading order, the system initially behaves like an RC circuit with a response time of $\lambda_D L / D$ (not $\lambda_D^2/D$), where $D$ is the ionic diffusivity, but nonlinearity violates this common picture and introduce multiple time scales. The charging process slows down, and neutral-salt adsorption by the diffuse part of the double layer couples to bulk diffusion at the time scale, $L^2/D$. In the ``strongly nonlinear'' regime (controlled by a dimensionless parameter resembling the Dukhin number), this effect produces bulk concentration gradients, and, at very large voltages, transient space charge. The article concludes with an overview of more general situations involving surface conduction, multi-component electrolytes, and Faradaic processes.Comment: 10 figs, 26 pages (double-column), 141 reference