Theoretical study of finite temperature spectroscopy in van der Waals clusters. II Time-dependent absorption spectra

Using approximate partition functions and a master equation approach, we investigate the statistical relaxation toward equilibrium in selected CaAr$_n$ clusters. The Gaussian theory of absorption (previous article) is employed to calculate the average photoabsorption intensity associated with the 4s^2-> 4s^14p^1 transition of calcium as a function of time during relaxation. In CaAr_6 and CaAr_10 simple relaxation is observed with a single time scale. CaAr_13 exhibits much slower dynamics and the relaxation occurs over two distinct time scales. CaAr_37 shows much slower relaxation with multiple transients, reminiscent of glassy behavior due to competition between different low-energy structures. We interpret these results in terms of the underlying potential energy surfaces for these clusters.Comment: 10 pages, 9 figure

Mechanical, Electrical, and Magnetic Properties of Ni Nanocontacts

The dynamic deformation upon stretching of Ni nanowires as those formed with mechanically controllable break junctions or with a scanning tunneling microscope is studied both experimentally and theoretically. Molecular dynamics simulations of the breaking process are performed. In addition, and in order to compare with experiments, we also compute the transport properties in the last stages before failure using the first-principles implementation of Landauer's formalism included in our transport package ALACANT.Comment: 5 pages, 6 figure

Sampling along reaction coordinates with the Wang-Landau method

The multiple range random walk algorithm recently proposed by Wang and Landau [Phys. Rev. Lett. 86, 2050 (2001)] is adapted to the computation of free energy profiles for molecular systems along reaction coordinates. More generally, we show how to extract partial averages in various statistical ensembles without invoking simulations with constraints, biasing potentials or unknown parameters. The method is illustrated on a model 10-dimensional potential energy surface, for which analytical results are obtained. It is then applied to the potential of mean force associated with the dihedral angle of the butane molecule in gas phase and in carbon tetrachloride solvent. Finally, isomerization in a small rocksalt cluster, Na4F4, is investigated in the microcanonical ensemble, and the results are compared to those of parallel tempering Monte Carlo.Comment: 6 pages, 5 figure

Analysis of the Kondo effect in ferromagnetic atomic-sized contacts

Atomic contacts made of ferromagnetic metals present zero-bias anomalies in the differential conductance due to the Kondo effect. These systems provide a unique opportunity to perform a statistical analysis of the Kondo parameters in nanostructures since a large number of contacts can be easily fabricated using break-junction techniques. The details of the atomic structure differ from one contact to another so a large number of different configurations can be statistically analyzed. Here we present such a statistical analysis of the Kondo effect in atomic contacts made from the ferromagnetic transition metals Ni, Co and Fe. Our analysis shows clear differences between materials that can be understood by fundamental theoretical considerations. This combination of experiments and theory allow us to extract information about the origin and nature of the Kondo effect in these systems and to explore the influence of geometry and valence in the Kondo screening of atomic-sized nanostructures.Comment: 17 pages, 11 figure

Measuring two-photon orbital angular momentum entanglement

We put forward an approach to estimate the amount of bipartite spatial entanglement of down-converted photon states correlated in orbital angular momentum and the magnitude of the transverse (radial) wave vectors. Both degrees of freedom are properly considered in our framework, which only requires azimuthal local linear optical transformations and mode selection analysis with two fiber detectors. The coincidence distributions predicted by our approach give an excellent fit to the distributions measured in a recent experiment aimed to show the very high-dimensional transverse entanglement of twin photons from a down-conversion source. Our estimate for the Schmidt number is substantially lower but still confirms the presence of high-dimensional entanglement.Comment: Extended paper of a published version in PRA, with some extra appendice

Grand and Semigrand Canonical Basin-Hopping.

We introduce grand and semigrand canonical global optimization approaches using basin-hopping with an acceptance criterion based on the local contribution of each potential energy minimum to the (semi)grand potential. The method is tested using local harmonic vibrational densities of states for atomic clusters as a function of temperature and chemical potential. The predicted global minima switch from dissociated states to clusters for larger values of the chemical potential and lower temperatures, in agreement with the predictions of a model fitted to heat capacity data for selected clusters. Semigrand canonical optimization allows us to identify particularly stable compositions in multicomponent nanoalloys as a function of increasing temperature, whereas the grand canonical potential can produce a useful survey of favorable structures as a byproduct of the global optimization search.FC acknowledges generous computational resources granted by the regional Pôle Scientifique de Modélisation Numérique in Lyon. DJW and DS acknowledge financial support from the EPSRC and the ERC.This is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/acs.jctc.5b0096