Solvation in atomic liquids: connection between Gaussian field theory and density functional theory

For the problem of molecular solvation, formulated as a liquid submitted to the external potential field created by a molecular solute of arbitrary shape dissolved in that solvent, we draw a connection between the Gaussian field theory derived by David Chandler [Phys. Rev. E, 1993, 48, 2898] and classical density functional theory. We show that Chandler's results concerning the solvation of a hard core of arbitrary shape can be recovered by either minimising a linearised HNC functional using an auxiliary Lagrange multiplier field to impose a vanishing density inside the core, or by minimising this functional directly outside the core --- indeed a simpler procedure. Those equivalent approaches are compared to two other variants of DFT, either in the HNC, or partially linearised HNC approximation, for the solvation of a Lennard-Jones solute of increasing size in a Lennard-Jones solvent. Compared to Monte-Carlo simulations, all those theories give acceptable results for the inhomogeneous solvent structure, but are completely out-of-range for the solvation free-energies. This can be fixed in DFT by adding a hard-sphere bridge correction to the HNC functional.Comment: 14 pages, 4 figure

Molecular hydrodynamics from memory kernels

The memory kernel for a tagged particle in a fluid, computed from molecular dynamics simulations, decays algebraically as t−3/2. We show how the hydrodynamic Basset-Boussinesq force naturally emerges from this long-time tail and generalize the concept of hydrodynamic added mass. This mass term is negative in the present case of a molecular solute, which is at odds with incompressible hydrodynamics predictions. Lastly, we discuss the various contributions to the friction, the associated time scales, and the crossover between the molecular and hydrodynamic regimes upon increasing the solute radius

Polarization control at the microscopic and electronic structure observatory

The new Microscopic and Electronic Structure Observatory (MAESTRO) at the Advanced Light Source (ALS) in Berkeley provides X-rays of variable polarization, produced by an elliptically polarized undulator (EPU), for angle resolved photoemission (ARPES) and photoemission electron microscopy (PEEM) experiments. The interpretation of photoemission data, in particular of dichroism effects in ARPES, requires the precise knowledge of the exact polarization state. Numerical simulations show that the first harmonics of the EPU at MAESTRO provides soft X-rays of almost 100% on axis polarization. However, the higher harmonics as well as the downstream optical elements of the beamline, have a considerable impact on the polarization of the light delivered to the experimental end-station. Employing a simple reflective polarimeter, the polarization is characterized for variable EPU and beamline settings and the overall degree of polarization in the MAESTRO end-stations is estimated to be on the order of 83%

Diffusion coefficient and shear viscosity of rigid water models

We report the diffusion coefficient and viscosity of popular rigid water models: Two non polarizable ones (SPC/E with 3 sites, and TIP4P/2005 with 4 sites) and a polarizable one (Dang-Chang, 4 sites). We exploit the dependence of the diffusion coefficient on the system size [Yeh and Hummer, J. Phys. Chem. B 108, 15873 (2004)] to obtain the size-independent value. This also provides an estimate of the viscosity of all water models, which we compare to the Green-Kubo result. In all cases, a good agreement is found. The TIP4P/2005 model is in better agreement with the experimental data for both diffusion and viscosity. The SPC/E and Dang-Chang water overestimate the diffusion coefficient and underestimate the viscosity.Comment: 10 pages, 2 figures. To be published in J. Phys.: Condens. Matte

Dual character of the electronic structure in YBa2Cu4O8: conduction bands of CuO2 planes and CuO chains

We use microprobe Angle-Resolved Photoemission Spectroscopy (muARPES) to separately investigate the electronic properties of CuO2 planes and CuO chains in the high temperature superconductor, YBa2Cu4O8. In the CuO2 planes, a two dimensional (2D) electronic structure with nearly momentum independent bilayer splitting is observed. The splitting energy is 150 meV at (pi,0), almost 50% larger than in Bi2Sr2CaCu2O(8+d) and the electron scattering at the Fermi level in the bonding band is about 1.5 times stronger than in the antibonding band. The CuO chains have a quasi one dimensional (1D) electronic structure. We observe two 1D bands separated by ~ 550meV: a conducting band and an insulating band with an energy gap of ~ 240meV. We find that the conduction electrons are well confined within the planes and chains with a non-trivial hybridization.Comment: 4 pages, 4 figure

Jean-Pierre Hansen - a stimulating history of simulating fluids

International audienc

Quasiparticle Transformation During a Metal-Insulator Transition in Graphene

Here we show, with simultaneous transport and photoemission measurements, that the graphene terminated SiC(0001) surface undergoes a metal-insulator transition (MIT) upon dosingwith small amounts of atomic hydrogen. We find the room temperature resistance increases by about 4 orders of magnitude, a transition accompanied by anomalies in the momentum-resolved spectral function including a non-Fermi Liquid behaviour and a breakdown of the quasiparticle picture. These effects are discussed in terms of a possible transition to a strongly (Anderson) localized ground state.Comment: 11 pages, 4 figure

Cluster sum rules for three-body systems with angular-momentum dependent interactions

We derive general expressions for non-energy weighted and energy-weighted cluster sum rules for systems of three charged particles. The interferences between pairs of particles are found to play a substantial role. The energy-weighted sum rule is usually determined by the kinetic energy operator, but we demonstrate that it has similar additional contributions from the angular momentum and parity dependence of two- and three-body potentials frequently used in three-body calculations. The importance of the different contributions is illustrated with the dipole excitations in $^6$He. The results are compared with the available experimental data.Comment: 11 pages, 3 figures, 2 table