On the contact values of the density profiles in an electric double layer using density functional theory

A recently proposed local second contact value theorem [Henderson D., Boda D., J. Electroanal. Chem., 2005, 582, 16] for the charge profile of an electric double layer is used in conjunction with the existing Monte Carlo data from the literature to assess the contact behavior of the electrode-ion distributions predicted by the density functional theory. The results for the contact values of the co- and counterion distributions and their product are obtained for the symmetric valency, restricted primitive model planar double layer for a range of electrolyte concentrations and temperatures. Overall, the theoretical results satisfy the second contact value theorem reasonably well, the agreement with the simulations being semi-quantitative or better. The product of the co- and counterion contact values as a function of the electrode surface charge density is qualitative with the simulations with increasing deviations at higher concentrations.Comment: 10 pages, 8 figure

Sphaerodactylus vincenti

Number of Pages: 6Integrative BiologyGeological Science

Open-mindedness can decrease persuasion amongst adolescents: The role of self-affirmation

Objectives Self-affirmation (e.g., by reflecting on important personal values) has been found to promote more open-minded appraisal of threatening health messages in at-risk adults. However, it is unclear how self-affirmation affects adolescents and whether it has differential effects on the impact of these messages amongst those at relatively lower and higher risk. The current study explored moderation by risk. Design Participants were randomly assigned to either a self-affirmation or a control condition before receiving a health message concerning physical activity. Methods Older adolescents (N = 125) completed a self-affirmation or control writing task before reading about the health consequences of not meeting recommendations to be physically active for at least 60 min daily. Most of the sample did not achieve these levels of activity (98%, N = 123). Consequently, the message informed these participants that – unless they changed their behaviour – they would be at higher risk of heart disease. Participants completed measures of responses to the message and behaviour-specific cognitions (e.g., self-efficacy) for meeting the recommendations. Results For relatively inactive participants, self-affirmation was associated with increased persuasion. However, for those who were moderately active (but not meeting recommendations), those in the self-affirmation condition were less persuaded by the message. Conclusions Whilst self-affirmation can increase message acceptance, there are circumstances when the open-mindedness it induces may decrease persuasion. The evidence provided in this study suggests that caution may be needed when recommendations are challenging and it could be considered reasonable to be sceptical about the need to change behaviour

Influence of anisotropic ion shape, asymmetric valency, and electrolyte concentration on structural and thermodynamic properties of an electric double layer

Grand canonical Monte Carlo simulation results are reported for an electric double layer modelled by a planar charged hard wall, anisotropic shape cations, and spherical anions at different electrolyte concentrations and asymmetric valencies. The cations consist of two tangentially tethered hard spheres of the same diameter, $d$. One sphere is charged while the other is neutral. Spherical anions are charged hard spheres of diameter $d$. The ion valency asymmetry 1:2 and 2:1 is considered, with the ions being immersed in a solvent mimicked by a continuum dielectric medium at standard temperature. The simulations are carried out for the following electrolyte concentrations: 0.1, 1.0 and 2.0 M. Profiles of the electrode-ion, electrode-neutral sphere singlet distributions, the average orientation of dimers, and the mean electrostatic potential are calculated for a given electrode surface charge, $\sigma$, while the contact electrode potential and the differential capacitance are presented for varying electrode charge. With an increasing electrolyte concentration, the shape of differential capacitance curve changes from that with a minimum surrounded by maxima into that of a distorted single maximum. For a 2:1 electrolyte, the maximum is located at a small negative $\sigma$ value while for 1:2, at a small positive value.Comment: 10 pages, 6 figure

Double layer for hard spheres with an off-center charge

Simulations for the density and potential profiles of the ions in the planar electrical double layer of a model electrolyte or an ionic liquid are reported. The ions of a real electrolyte or an ionic liquid are usually not spheres; in ionic liquids, the cations are molecular ions. In the past, this asymmetry has been modelled by considering spheres that are asymmetric in size and/or valence (viz., the primitive model) or by dimer cations that are formed by tangentially touching spheres. In this paper we consider spherical ions that are asymmetric in size and mimic the asymmetrical shape through an off-center charge that is located away from the center of the cation spheres, while the anion charge is at the center of anion spheres. The various singlet density and potential profiles are compared to (i) the dimer situation, that is, the constituent spheres of the dimer cation are tangentially tethered, and (ii) the standard primitive model. The results reveal the double layer structure to be substantially impacted especially when the cation is the counterion. As well as being of intrinsic interest, this off-center charge model may be useful for theories that consider spherical models and introduce the off-center charge as a perturbation.Comment: 11 pages, 7 figure

An extended model of the quantum free-electron laser

Previous models of the quantum regime of operation of the Free Electron Laser (QFEL) have performed an averaging and the application of periodic boundary conditions to the coupled Maxwell - Schrodinger equations over short, resonant wavelength intervals of the interaction. Here, an extended, one-dimensional model of the QFEL interaction is presented in the absence of any such averaging or application of periodic boundary conditions, the absence of the latter allowing electron diffusion processes to be modeled throughout the pulse. The model is used to investigate how both the steady-state (CW) and pulsed regimes of QFEL operation are affected. In the steady-state regime it is found that the electrons are confined to evolve as a 2-level system, similar to the previous QFEL models. In the pulsed regime Coherent Spontaneous Emission (CSE) due to the shape of the electron pulse current distribution is shown to be present in the QFEL regime for the first time. However, unlike the classical case, CSE in the QFEL is damped by the effects of quantum diffusion of the electron wavefunction. Electron recoil from the QFEL interaction can also cause a diffusive drift between the recoiled and non-recoiled parts of the electron pulse wavefunction, effectively removing the recoiled part from the primary electron-radiation interaction.Comment: Submitted to Optics Expres

Orthogonal measurements are {\it almost} sufficient for quantum discord of two qubits

The common use in literature of orthogonal measurements in obtaining quantum discord for two-qubit states is discussed and compared with more general measurements. We prove the optimality of orthogonal measurements for rank 2 states. While for rank 3 and 4 mixed states they are not optimal, we present strong numerical evidence showing that they give the correct quantum discord up to minimal corrections. Based on the connection, through purification with an ancilla, between discord and entanglement of formation (EoF), we give a tight upper bound for the EoF of a $2\otimes N$ mixed state of rank 2, given by an optimal decomposition of 2 elements. We also provide an alternative way to compute the quantum discord for two qubits based on the Bloch vectors of the state.Comment: EPL 96, 40005 (2011

A Statistical Model for Simultaneous Template Estimation, Bias Correction, and Registration of 3D Brain Images

Template estimation plays a crucial role in computational anatomy since it provides reference frames for performing statistical analysis of the underlying anatomical population variability. While building models for template estimation, variability in sites and image acquisition protocols need to be accounted for. To account for such variability, we propose a generative template estimation model that makes simultaneous inference of both bias fields in individual images, deformations for image registration, and variance hyperparameters. In contrast, existing maximum a posterori based methods need to rely on either bias-invariant similarity measures or robust image normalization. Results on synthetic and real brain MRI images demonstrate the capability of the model to capture heterogeneity in intensities and provide a reliable template estimation from registration