A fully quantum mechanical calculation of the diffusivity of hydrogen in iron using the tight binding approximation and path integral theory

We present calculations of free energy barriers and diffusivities as functions of temperature for the diffusion of hydrogen in bcc-Fe. This is a fully quantum mechanical approach since the total energy landscape is computed using a new self consistent, transferable tight binding model for interstitial impurities in magnetic iron. Also the hydrogen nucleus is treated quantum mechanically and we compare here two approaches in the literature both based in the Feynman path integral formulation of statistical mechanics. We find that the quantum transition state theory which admits greater freedom for the proton to explore phase space gives result in better agreement with experiment than the alternative which is based on fixed centroid calculations of the free energy barrier. We also find results in better agreement compared to recent centroid molecular dynamics (CMD) calculations of the diffusivity which employed a classical interatomic potential rather than our quantum mechanical tight binding theory. In particular we find first that quantum effects persist to higher temperatures than previously thought, and conversely that the low temperature diffusivity is smaller than predicted in CMD calculations and larger than predicted by classical transition state theory. This will have impact on future modeling and simulation of hydrogen trapping and diffusion

Spectroscopy of the a^3\Sigma_u^+ state and the coupling to the X^1\Sigma_g^+ state of K_2

We report on high resolution Fourier-transform spectroscopy of fluorescence to the a^3\Sigma_u^+ state excited by two-photon or two-step excitation from the X^1\Sigma_g^+ state to the 2^3\Pi_g state in the molecule K_2. These spectroscopic data are combined with recent results of Feshbach resonances and two-color photoassociation spectra for deriving the potential curves of X^1\Sigma_g^+ and a^3\Sigma_u^+ up to the asymptote. The precise relative position of the triplet levels with respect of the singlet levels was achieved by including the excitation energies from the X^1\Sigma_g^+ state to the 2^3\Pi_g state and down to the a^3\Sigma_u^+ state in the simultaneous fit of both potentials. The derived precise potential curves allow for reliable modeling of cold collisions of pairs of potassium atoms in their ^2S ground state

Experimental study of the Ca2 1S+1S asymptote

The filtered laser excitation technique was applied for measuring transition frequencies of the Ca$_2$ B-X system from asymptotic levels of the X$^1\Sigma_{\mathrm g}^{+}$ ground state reaching $v''=38$. That level has an outer classical turning point of about 20~\AA which is only 0.2 \rcm below the molecular $^1$S$+^1$S asymptote. Extensive analysis of the spectroscopic data, involving Monte Carlo simulation, allowed for a purely experimental determination of the long range parameters of the potential energy curve. The possible values of the s-wave scattering length could be limited to be between 250$a_0$ and 1000$a_0$.Comment: 10 pages, 7 figure

Metal-insulator transition in copper oxides induced by apex displacements

High temperature superconductivity has been found in many kinds of compounds built from planes of Cu and O, separated by spacer layers. Understanding why critical temperatures are so high has been the subject of numerous investigations and extensive controversy. To realize high temperature superconductivity, parent compounds are either hole-doped, such as {La$_{2}$CuO$_4$} (LCO) with Sr (LSCO), or electron doped, such as {Nd$_{2}$CuO$_4$} (NCO) with Ce (NCCO). In the electron doped cuprates, the antiferromagnetic phase is much more robust than the superconducting phase. However, it was recently found that the reduction of residual out-of-plane apical oxygens dramatically affects the phase diagram, driving those compounds to a superconducting phase. Here we use a recently developed first principles method to explore how displacement of the apical oxygen (A-O) in LCO affects the optical gap, spin and charge susceptibilities, and superconducting order parameter. By combining quasiparticle self-consistent GW (QS\emph{GW}) and dynamical mean field theory (DMFT), that LCO is a Mott insulator; but small displacements of the apical oxygens drive the compound to a metallic state through a localization/delocalization transition, with a concomitant maximum $d$-wave order parameter at the transition. We address the question whether NCO can be seen as the limit of LCO with large apical displacements, and elucidate the deep physical reasons why the behaviour of NCO is so different than the hole doped materials. We shed new light on the recent correlation observed between T$_c$ and the charge transfer gap, while also providing a guide towards the design of optimized high-Tc superconductors. Further our results suggest that strong correlation, enough to induce Mott gap, may not be a prerequisite for high-Tc superconductivity

Self-energies in itinerant magnets: A focus on Fe and Ni

We present a detailed study of local and non-local correlations in the electronic structure of elemental transition metals carried out by means of the Quasiparticle Self-consistent GW (QSGW ) and Dynamical Mean Field Theory (DMFT). Recent high resolution ARPES and Haas-van Alphen data of two typical transition metal systems (Fe and Ni) are used as case study. (i) We find that the properties of Fe are very well described by QSGW. Agreement with cyclotron and very clean ARPES measurements is excellent, provided that final-state scattering is taken into account. This establishes the exceptional reliability of QSGW also in metallic systems. (ii) Nonetheless QSGW alone is not able to provide an adequate description of the Ni ARPES data due to strong local spin fluctuations. We surmount this deficiency by combining nonlocal charge fluctuations in QSGW with local spin fluctuations in DMFT (QSGW + 'Magnetic DMFT'). (iii) Finally we show that the dynamics of the local fluctuations are actually not crucial. The addition of an external static field can lead to similarly good results if non-local correlations are included through QSGW

The coupling of the X1Σ+^{1}\Sigma ^{+} and a3Σ+^{3}\Sigma ^{+} states of KRb

A comprehensive study of the electronic states at the 4s+5s asymptote in KRb is presented. Abundant spectroscopic data on the \astate state were collected by Fourier-transform spectroscopy which allow to determine an accurate experimental potential energy curve up to 14.8 \AA . The existing data set (C. Amiot et al. J. Chem. Phys. 112, 7068 (2000)) on the ground state \Xstate was extended by several additional levels lying close to the atomic asymptote. In a coupled channels fitting routine complete molecular potentials for both electronic states were fitted. Along with the line frequencies of the molecular transitions, recently published positions of Feshbach resonances in $^{40}$K and $^{87}$Rb mixtures (F. Ferlaino et al. Phys. Rev. A 74, 039903 (2006)) were included in the fit. This makes the derived potential curves capable for an accurate description of observed cold collision features so far. Predictions of scattering lengths and Feshbach resonances in other isotopic combinations are reported.Comment: 14 pages, 5 figure

Interatomic potentials of van der Waals dimers Hg2Hg_{2} and Cd2Cd_{2} : probing discrepancies between theory and experiment

Results of new all-electron ab initio calculations and revisit of experimental studies of the interatomic potentials of lower-lying ungerade excited and ground electronic energy states of the Hg_{2} and Cd_{2} van der Waals complexes are used as probes of discrepancies between theory and experiment. From simulations of the previously and presently measured LIF excitation and dispersed emission spectra new analytical representations of the excited- and the ground-state interatomic potentials are proposed. An inverted perturbation approach was also used to improve the studied interatomic potentials. The comparison of the new ab-initio calculated potentials with the results of the analyses illustrates an improve theory-to-experiment agreement for such a demanding system like Hg_{2} or Cd_{2}