Frequency shift of hyperfine transitions due to blackbody radiation

We have performed calculations of the size of the frequency shift induced by a static electric field on the clock transition frequencies of the hyperfine splitting in Yb+, Rb, Cs, Ba+, and Hg+. The calculations are used to find the frequency shifts due to blackbody radiation which are needed for accurate frequency measurements and improvements of the limits on variation of the fine structure constant, alpha. Our result for Cs (delta nu E^2=-2.26 times 10^{-10}Hz/(V/m)^2) is in good agreement with early measurements and ab initio calculations. We present arguments against recent claims that the actual value might be smaller. The difference (approx 10%) is due to the contribution of the continuum spectrum in the sum over intermediate states.Comment: Added discussion of Cs results and reference

Water exchange at a hydrated platinum electrode is rare and collective

We use molecular dynamics simulations to study the exchange kinetics of water molecules at a model metal electrode surface -- exchange between water molecules in the bulk liquid and water molecules bound to the metal. This process is a rare event, with a mean residence time of a bound water of about 40 ns for the model we consider. With analysis borrowed from the techniques of rare-event sampling, we show how this exchange or desorption is controlled by (1) reorganization of the hydrogen bond network within the adlayer of bound water molecules, and by (2) interfacial density fluctuations of the bulk liquid adjacent to the adlayer. We define collective coordinates that describe the desorption mechanism. Spatial and temporal correlations associated with a single event extend over nanometers and tens of picoseconds.Comment: 10 pages, 9 figure

The role of alkane coordination in C–H bond cleavage at a Pt(II) center

The rates of CFormula H bond activation for various alkanes by [(N–N)Pt(Me)(TFEd3)]+ (N Formula N = ArFormula NFormula C(Me)Formula C(Me)Formula NFormula Ar; Ar = 3,5-di-tert-butylphenyl; TFE-d3 = CF3CD2OD) were studied. Both linear and cyclic alkanes give the corresponding alkene-hydride cation [(N–N)Pt(H)(alkene)]+ via (i) rate determining alkane coordination to form a CFormula H {sigma} complex, (ii) oxidative cleavage of the coordinated CFormula H bond to give a platinum(IV) alkyl-methyl-hydride intermediate, (iii) reductive coupling to generate a methane {sigma} complex, (iv) dissociation of methane, and (v) beta-H elimination to form the observed product. Second-order rate constants for cycloalkane activation (CnH2n), are proportional to the size of the ring (k ~ n). For cyclohexane, the deuterium kinetic isotope effect (kH/kD) of 1.28 (5) is consistent with the proposed rate determining alkane coordination to form a CFormula H {sigma} complex. Statistical scrambling of the five hydrogens of the Pt-methyl and the coordinated methylene unit, via rapid, reversible steps ii and iii, and interchange of geminal CFormula H bonds of the methane and cyclohexane CFormula H {sigma} adducts, is observed before loss of methane

Determination of the basic timescale in kinetic Monte Carlo simulations by comparison with cyclic-voltammetry experiments

While kinetic Monte Carlo simulations can provide long-time simulations of the dynamics of physical and chemical systems, it is not yet possible in general to identify the inverse Monte Carlo attempt frequency with a physical timescale. Here we demonstrate such an identification by comparing simulations with experimental data. Using a dynamic lattice-gas model for the electrosorption of Br on Ag(100), we measure the scan-rate dependence of the separation between positive-and negative-going peaks in cyclic-voltammetry (CV) and compare simulated and experimental peak separations. By adjusting the Monte Carlo attempt frequency, good agreement between simulated and experimental peak separations is achieved. It is also found that the uniqueness of such a determination is dependent on the relative values of the adsorption/desorption and diffusion free-energy barriers.Comment: Accepted for publication in Surface Science Letters,8 pages, 4 figure

The parity-violating pion-nucleon coupling constant from a realistic three flavor Skyrme model

We study the parity-violating pion-nucleon coupling $G_\pi$ in the framework of a realistic three flavor Skryme model. We find a sizeable enhancement of $G_\pi \simeq 0.8 ... 1.3 \cdot 10^{-7}$ compared to previous calculations in two-flavor models with vector mesons. This strangeness enhancement stems from induced kaon fields of the chiral soliton and the non-monotoneous dependence on symmetry breaking of the nucleon matrix element of the flavor singlet piece of the operator associated with these induced fields. Both features are sensitive to four quark operators including an $\bar s s$ pair.Comment: 10 pp, LaTeX, uses epsf, 2 figs, small corrections plus additional explanations, value of Gpi somewhat smalle

Nonlocal reflection by photonic barriers

The time behaviour of microwaves undergoing partial reflection by photonic barriers was measured in the time and in the frequency domain. It was observed that unlike the duration of partial reflection by dielectric layers, the measured reflection duration of barriers is independent of their length. The experimental results point to a nonlocal behaviour of evanescent modes at least over a distance of some ten wavelengths. Evanescent modes correspond to photonic tunnelling in quantum mechanics.Comment: 8 pages, 5 figure

Immediate or delayed breast reconstruction after mastectomy: what do women really want

Breast reconstruction, especially immediate reconstruction after mastectomy has increased over the last decades, at present being regularly offered in many centres worldwide. Despite obvious benefits and the evident oncological safety of primary breast reconstruction, the majority of women still receive a delayed procedure or even no reconstructive surgery. The objective of the present study was to determine the preference of women for breast reconstruction—immediate or delayed—and in the case of rejection of treatment to find out the reasons for this reluctance. In a prospective study a sample of 200 women—divided into two groups—were evaluated by an oral interview on the subject. The two-formed groups of participants consisted of randomly chosen women (n=100) and non-surgical nurses (n=100). The questionnaire surveyed personal data including marital status and educational level, as well as information about the preferred timing, the method of and the reasons for or against breast reconstruction. The evaluation of all data showed that 66% of the participants voted for additional surgery after mastectomy. Young age and high education level were significantly correlated (age r=0.56, P<0.01; education r=0.25, P<0.01) to the wish for reconstruction. The mean age of all participants was 39years (range 20-69), with a significant difference between the two groups (P<0.01), the group of nurses being younger (mean age 35, range 20-62) and the other women being older (mean age 43, range 20-69). Concerning the timing of reconstruction, 21% of women elected to have an immediate and 27% a delayed operation. Yet, 52% could not come to a decision as to whether they should prefer a primary or secondary procedure. For the surgical procedure—autologous versus non-autologous tissue—about 23% of the participants could not decide spontaneously, while 40% preferred autologous tissue, 14% implants and 23% would choose a combination of both. The main reason in favour of reconstruction was that it would enhance the physical appearance (96%), whereas an important reason for general rejection was the fear of additional surgical risk (19%). For primary reconstruction, a high percentage of women also were highly concerned that reconstruction could mask cancer recurrence (62%). Although the majority of women—unaffected with breast cancer—are interested in breast reconstruction, more than half of them cannot decide spontaneously about the timing and mode of surgery, including the medical women. The collected data emphasize the urgent necessity to systematically inform women and the whole population about the options of breast reconstruction. Equally important is for the involved surgeons to know the individual wishes and fears of women unexpectedly confronted with the diagnosis of breast cancer in order to provide comprehensive preoperative counselling with respect to cancer therapy including breast reconstructio

Nonlinear Dynamics of Capacitive Charging and Desalination by Porous Electrodes

The rapid and efficient exchange of ions between porous electrodes and aqueous solutions is important in many applications, such as electrical energy storage by super-capacitors, water desalination and purification by capacitive deionization (or desalination), and capacitive extraction of renewable energy from a salinity difference. Here, we present a unified mean-field theory for capacitive charging and desalination by ideally polarizable porous electrodes (without Faradaic reactions or specific adsorption of ions) in the limit of thin double layers (compared to typical pore dimensions). We illustrate the theory in the case of a dilute, symmetric, binary electrolyte using the Gouy-Chapman-Stern (GCS) model of the double layer, for which simple formulae are available for salt adsorption and capacitive charging of the diffuse part of the double layer. We solve the full GCS mean-field theory numerically for realistic parameters in capacitive deionization, and we derive reduced models for two limiting regimes with different time scales: (i) In the "super-capacitor regime" of small voltages and/or early times where the porous electrode acts like a transmission line, governed by a linear diffusion equation for the electrostatic potential, scaled to the RC time of a single pore. (ii) In the "desalination regime" of large voltages and long times, the porous electrode slowly adsorbs neutral salt, governed by coupled, nonlinear diffusion equations for the pore-averaged potential and salt concentration

The Use of the Health of the Nation Outcome Scales for Assessing Functional Change in Treatment Outcome Monitoring of Patients with Chronic Schizophrenia.

Schizophrenia is a severe mental disorder that is characterized not only by symptomatic severity but also by high levels of functional impairment. An evaluation of clinical outcome in treatment of schizophrenia should therefore target not only assessing symptom change but also alterations in functioning. This study aimed to investigate whether there is an agreement between functional- and symptom-based outcomes in a clinical sample of admissions with chronic forms of schizophrenia. A full 3-year cohort of consecutive inpatient admissions for schizophrenia (N = 205) was clinically rated with the Positive and Negative Symptom Scale (PANSS) and the Health of the Nation Outcome Scales (HoNOS) as measures of functioning at the time of admission and discharge. The sample was stratified twofold: first, according to the degree of PANSS symptom improvement during treatment with the sample being divided into three treatment response groups: non-response, low response, and high response. Second, achievement of remission was defined using the Remission in Schizophrenia Working Group criteria based on selected PANSS symptoms. Repeated measures analyses were used to compare the change of HoNOS scores over time across groups. More than a half of all admissions achieved a symptom reduction of at least 20% during treatment and around one quarter achieved remission at discharge. Similarly, HoNOS scores improved significantly between admission and discharge. Interaction analyses indicated higher functional improvements to be associated with increasing levels of treatment response. Functional improvement in individuals treated for schizophrenia was linked to a better clinical outcome, which implies a functional association. Thus, improvement of functioning represents an important therapeutic target in the treatment of schizophrenia

The performance of the Health of the Nation Outcome Scales as measures of clinical severity.

The aim of this study was to examine the performance of the Health of the Nation Outcome Scales (HoNOS) against other measures of functioning and mental health in a full three-year cohort of admissions to a psychiatric hospital. A sample of N=1719 patients (35.3% females, aged 17-78 years) was assessed using observer-rated measures and self-reports of psychopathology at admission. Self-reports were available from 51.7% of the sample (34.4% females, aged 17-76 years). Functioning and psychopathology were compared across five ICD-10 diagnostic groups: substance use disorders, schizophrenia and psychotic disorders, affective disorders, anxiety/somatoform disorders and personality disorders. Associations between the measures were examined, stratifying by diagnostic subgroup. The HoNOS were strongly linked to other measures primarily in psychotic disorders (except for the behavioral subscale), while those with substance use disorders showed rather poor links. Those with anxiety/somatoform disorders showed null or only small associations. This study raises questions about the overall validity of the HoNOS. It seems to entail different levels of validity when applied to different diagnostic groups. In clinical practice the HoNOS should not be used as a stand-alone instrument to assess outcome but rather as part of a more comprehensive battery including diagnosis-specific measures