Superprotonic phase transition of CsHSO4: A molecular dynamics simulation study

The superprotonic phase transition (phase II --> phase I; 414 K) of cesium hydrogen sulfate, CsHSO4, was simulated using molecular dynamics with the "first principles" MSXX force field (FF). The structure, binding energy, and vibrational frequencies of the CsHSO4 monomer, the binding energy of the (H2SO4)2 dimer, and the torsion barrier of the HSO4- ion were determined from quantum mechanical calculations, and the parameters of the Dreiding FF for Cs, S, O, and H adjusted to reproduce these quantities. Each hydrogen atom was treated as bonded exclusively to a single oxygen atom (proton donor), but allowed to form hydrogen bonds to various second nearest oxygen atoms (proton acceptors). Fixed temperature-pressure (NPT) dynamics were employed to study the structure as a function of temperature from 298 to 723 K. In addition, the influence of several force field parameters, including the hydrogen torsional barrier height, hydrogen bond strength, and oxygen charge distribution, on the structural behavior of CsHSO4 was probed. Although the FF does not allow proton migration (i.e., proton jumps) between oxygen atoms, a clear phase transition occurred as demonstrated by a discrete change of unit cell symmetry (monoclinic to tetragonal), cell volume, and molar enthalpy. The dynamics of the HSO4- group reorientational motion also changed dramatically at the transition. The observation of a transition to the expected tetragonal phase using a FF in which protons cannot migrate indicates that proton diffusion does not drive the transition to the superprotonic phase. Rather, high conductivity is a consequence of the rapid reorientations that occur in the high temperature phase. Furthermore, because no input from the superprotonic phase was employed in these simulations, it may be possible to employ MD to hypothesize superprotonic materials

Free energy barrier for molecular motions in bistable [2]rotaxane molecular electronic devices

Donor−acceptor binding of the π-electron-poor cyclophane cyclobis(paraquat-p-phenylene) (CBPQT^(4+)) with the π-electron-rich tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) stations provides the basis for electrochemically switchable, bistable [2]rotaxanes, which have been incorporated and operated within solid-state devices to form ultradense memory circuits (ChemPhysChem 2002, 3, 519−525; Nature 2007, 445, 414−417) and nanoelectromechanical systems. The rate of CBPQT^(4+) shuttling at each oxidation state of the [2]rotaxane dictates critical write-and-retention time parameters within the devices, which can be tuned through chemical synthesis. To validate how well computational chemistry methods can estimate these rates for use in designing new devices, we used molecular dynamics simulations to calculate the free energy barrier for the shuttling of the CBPQT^4+ ring between the TTF and the DNP. The approach used here was to calculate the potential of mean force along the switching pathway, from which we calculated free energy barriers. These calculations find a turn-on time after the rotaxane is doubly oxidized of ~10^9−7) s (suggesting that the much longer experimental turn-on time is determined by the time scale of oxidization). The return barrier from the DNP to the TTF leads to a predicted lifetime of 2.1 s, which is compatible with experiments

Dynamical dark energy: Current constraints and forecasts

We consider how well the dark energy equation of state $w$ as a function of red shift $z$ will be measured using current and anticipated experiments. We use a procedure which takes fair account of the uncertainties in the functional dependence of $w$ on $z$, as well as the parameter degeneracies, and avoids the use of strong prior constraints. We apply the procedure to current data from WMAP, SDSS, and the supernova searches, and obtain results that are consistent with other analyses using different combinations of data sets. The effects of systematic experimental errors and variations in the analysis technique are discussed. Next, we use the same procedure to forecast the dark energy constraints achieveable by the end of the decade, assuming 8 years of WMAP data and realistic projections for ground-based measurements of supernovae and weak lensing. We find the $2 \sigma$ constraints on the current value of $w$ to be $\Delta w_0 (2 \sigma) = 0.20$, and on $dw/dz$ (between $z=0$ and $z=1$) to be $\Delta w_1 (2 \sigma)=0.37$. Finally, we compare these limits to other projections in the literature. Most show only a modest improvement; others show a more substantial improvement, but there are serious concerns about systematics. The remaining uncertainty still allows a significant span of competing dark energy models. Most likely, new kinds of measurements, or experiments more sophisticated than those currently planned, are needed to reveal the true nature of dark energy.Comment: 24 pages, 20 figures. Added SN systematic uncertainties, extended discussio

On the existence of solutions to the relativistic Euler equations in 2 spacetime dimensions with a vacuum boundary

We prove the existence of a wide class of solutions to the isentropic relativistic Euler equations in 2 spacetime dimensions with an equation of state of the form $p=K\rho^2$ that have a fluid vacuum boundary. Near the fluid vacuum boundary, the sound speed for these solutions are monotonically decreasing, approaching zero where the density vanishes. Moreover, the fluid acceleration is finite and bounded away from zero as the fluid vacuum boundary is approached. The existence results of this article also generalize in a straightforward manner to equations of state of the form $p=K\rho^\frac{\gamma+1}{\gamma}$ with $\gamma > 0$.Comment: A major revision of the second half of the pape

Isometric Representations of Totally Ordered Semigroups

Let S be a subsemigroup of an abelian torsion-free group G. If S is a positive cone of G, then all C*-algebras generated by faithful isometrical non-unitary representations of S are canonically isomorphic. Proved by Murphy, this statement generalized the well-known theorems of Coburn and Douglas. In this note we prove the reverse. If all C*-algebras generated by faithful isometrical non-unitary representations of S are canonically isomorphic, then S is a positive cone of G. Also we consider G = Z\times Z and prove that if S induces total order on G, then there exist at least two unitarily not equivalent irreducible isometrical representation of S. And if the order is lexicographical-product order, then all such representations are unitarily equivalent.Comment: February 21, 2012. Kazan, Russi

B -> Xs l_i^+ l_j^+ Decays with R-parity Violation

We derive the upper bounds on certain products of R-parity- and lepton-flavor-violating couplings from B \ra X_s {l_i}^+ {l_j}^- decays. These modes of B-meson decays can constrain the product combinations of the couplings with one or more heavy generation indices which are comparable with or stronger than the present bounds. From the studies of the invariant dilepton mass spectrum and the forward backward asymmetry of the emitted leptons we note the possibility of detecting R-parity-violating signals even when the total decay rate due to R-parity violating couplings is comparable with that in the standard model and discriminating two types of R-parity-violating signals. The general expectation of the enhancement of the forward backward asymmetry of the emitted leptons in the minimal supersymmetric standard model with R-parity may be corrupted by R-parity violation.Comment: 10 pages, Revtex, 1 table and 2 figure

Living IoT: A Flying Wireless Platform on Live Insects

Sensor networks with devices capable of moving could enable applications ranging from precision irrigation to environmental sensing. Using mechanical drones to move sensors, however, severely limits operation time since flight time is limited by the energy density of current battery technology. We explore an alternative, biology-based solution: integrate sensing, computing and communication functionalities onto live flying insects to create a mobile IoT platform. Such an approach takes advantage of these tiny, highly efficient biological insects which are ubiquitous in many outdoor ecosystems, to essentially provide mobility for free. Doing so however requires addressing key technical challenges of power, size, weight and self-localization in order for the insects to perform location-dependent sensing operations as they carry our IoT payload through the environment. We develop and deploy our platform on bumblebees which includes backscatter communication, low-power self-localization hardware, sensors, and a power source. We show that our platform is capable of sensing, backscattering data at 1 kbps when the insects are back at the hive, and localizing itself up to distances of 80 m from the access points, all within a total weight budget of 102 mg.Comment: Co-primary authors: Vikram Iyer, Rajalakshmi Nandakumar, Anran Wang, In Proceedings of Mobicom. ACM, New York, NY, USA, 15 pages, 201

Jost Function for Singular Potentials

An exact method for direct calculation of the Jost function and Jost solutions for a repulsive singular potential is presented. Within this method the Schrodinger equation is replaced by an equivalent system of linear first-order differential equations, which after complex rotation, can easily be solved numerically. The Jost function can be obtained to any desired accuracy for all complex momenta of physical interest, including the spectral points corresponding to bound and resonant states. The method can also be used in the complex angular-momentum plane to calculate the Regge trajectories. The effectiveness of the method is demonstrated using the Lennard-Jones (12,6) potential. The spectral properties of the realistic inter-atomic He4-He4 potentials HFDHE2 and HFD-B of Aziz and collaborators are also investigated.Comment: 12 pages, latex, 2 eps-figures, submitted to Phys.Rev.

The area of horizons and the trapped region

This paper considers some fundamental questions concerning marginally trapped surfaces, or apparent horizons, in Cauchy data sets for the Einstein equation. An area estimate for outermost marginally trapped surfaces is proved. The proof makes use of an existence result for marginal surfaces, in the presence of barriers, curvature estimates, together with a novel surgery construction for marginal surfaces. These results are applied to characterize the boundary of the trapped region.Comment: 44 pages, v3: small changes in presentatio