Variational Monte Carlo for spin-orbit interacting systems

Recently, a diffusion Monte Carlo algorithm was applied to the study of spin dependent interactions in condensed matter. Following some of the ideas presented therein, and applied to a Hamiltonian containing a Rashba-like interaction, a general variational Monte Carlo approach is here introduced that treats in an efficient and very accurate way the spin degrees of freedom in atoms when spin orbit effects are included in the Hamiltonian describing the electronic structure. We illustrate the algorithm on the evaluation of the spin-orbit splittings of isolated carbon and lead atoms. In the case of the carbon atom, we investigate the differences between the inclusion of spin-orbit in its realistic and effective spherically symmetrized forms. The method exhibits a very good accuracy in describing the small energy splittings, opening the way for a systematic quantum Monte Carlo studies of spin-orbit effects in atomic systems.Comment: 7 pages, 0 figure

Van der Waals Interactions in DFT using Wannier Functions: improved C6C_6 and C3C_3 coefficients by a new approach

A new implementation is proposed for including van der Waals interactions in Density Functional Theory using the Maximally-Localized Wannier functions. With respect to the previous DFT/vdW-WF method, the present DFT/vdW-WF2 approach, which is based on the simpler London expression and takes into account the intrafragment overlap of the localized Wannier functions, leads to a considerable improvement in the evaluation of the $C_6$ van der Waals coefficients, as shown by the application to a set of selected dimers. Preliminary results on Ar on graphite and Ne on the Cu(111) metal surface suggest that also the $C_3$ coefficients, characterizing molecule-surfaces van der Waals interactions are better estimated with the new scheme.Comment: 5 pages, 2 table

Adsorption of rare-gas atoms on Cu(111) and Pb(111) surfaces by van der Waals-corrected Density Functional Theory

The DFT/vdW-WF method, recently developed to include the Van der Waals interactions in Density Functional Theory (DFT) using the Maximally Localized Wannier functions, is applied to the study of the adsorption of rare-gas atoms (Ne, Ar, Kr, and Xe) on the Cu(111) and Pb(111) surfaces, at three high-symmetry sites. We evaluate the equilibrium binding energies and distances, and the induced work-function changes and dipole moments. We find that, for Ne, Ar, and Kr on the Cu(111) surface the different adsorption configurations are characterized by very similar binding energies, while the favored adsorption site for Xe on Cu(111) is on top of a Cu atom, in agreement with previous theoretical calculations and experimental findings, and in common with other close-packed metal surfaces. Instead, the favored site is always the hollow one on the Pb(111) surface, which therefore represents an interesting system where the investigation of high-coordination sites is possible. Moreover, the Pb(111) substrate is subject, upon rare-gas adsorption, to a significantly smaller change in the work function (and to a correspondingly smaller induced dipole moment) than Cu(111). The role of the chosen reference DFT functional and of different Van der Waals corrections, and their dependence on different rare-gas adatoms, are also discussed

Exponential decay properties of Wannier functions and related quantities

The spatial decay properties of Wannier functions and related quantities have been investigated using analytical and numerical methods. We find that the form of the decay is a power law times an exponential, with a particular power-law exponent that is universal for each kind of quantity. In one dimension we find an exponent of -3/4 for Wannier functions, -1/2 for the density matrix and for energy matrix elements, and -1/2 or -3/2 for different constructions of non-orthonormal Wannier-like functions.Comment: 4 pages, with 3 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/lh_wann/index.htm

Adsorption of benzene on Si(100) from first principles

Adsorption of benzene on the Si(100) surface is studied from first principles. We find that the most stable configuration is a tetra-$\sigma$-bonded structure characterized by one C-C double bond and four C-Si bonds. A similar structure, obtained by rotating the benzene molecule by 90 degrees, lies slightly higher in energy. However, rather narrow wells on the potential energy surface characterize these adsorption configurations. A benzene molecule impinging on the Si surface is most likely to be adsorbed in one of three different di-$\sigma$-bonded, metastable structures, characterized by two C-Si bonds, and eventually converts into the lowest-energy configurations. These results are consistent with recent experiments.Comment: 4 pages, RevTex, 2 PostScript gzipped figure

Calculations of the A_1 phonon frequency in photoexcited Tellurium

Calculations of the A_1 phonon frequency in photoexcited tellurium are presented. The phonon frequency as a function of photoexcited carrier density and phonon amplitude is determined. Recent pump probe experiments are interpreted in the light of these calculatons. It is proposed that, in conjunction with measurements of the phonon period in ultra-fast pump-probe reflectivity experiments, the calculated frequency shifts can be used to infer the evolution of the density of photoexcited carriers on a sub-picosecond time-scale.Comment: 15 pages Latex, 3 postscript figure

Theory for the ultrafast ablation of graphite films

The physical mechanisms for damage formation in graphite films induced by femtosecond laser pulses are analyzed using a microscopic electronic theory. We describe the nonequilibrium dynamics of electrons and lattice by performing molecular dynamics simulations on time-dependent potential energy surfaces. We show that graphite has the unique property of exhibiting two distinct laser induced structural instabilities. For high absorbed energies (> 3.3 eV/atom) we find nonequilibrium melting followed by fast evaporation. For low intensities above the damage threshold (> 2.0 eV/atom) ablation occurs via removal of intact graphite sheets.Comment: 5 pages RevTeX, 3 PostScript figures, submitted to Phys. Re

Wannier-function description of the electronic polarization and infrared absorption of high-pressure hydrogen

We have constructed maximally-localized Wannier functions for prototype structures of solid molecular hydrogen under pressure, starting from LDA and tight-binding Bloch wave functions. Each occupied Wannier function can be associated with two paired protons, defining a ``Wannier molecule''. The sum of the dipole moments of these ``molecules'' always gives the correct macroscopic polarization, even under strong compression, when the overlap between nearby Wannier functions becomes significant. We find that at megabar pressures the contributions to the dipoles arising from the overlapping tails of the Wannier functions is very large. The strong vibron infrared absorption experimentally observed in phase III, above ~ 150 GPa, is analyzed in terms of the vibron-induced fluctuations of the Wannier dipoles. We decompose these fluctuations into ``static'' and ``dynamical'' contributions, and find that at such high densities the latter term, which increases much more steeply with pressure, is dominant.Comment: 17 pages, two-column style with 14 postscript figures embedded. Uses REVTEX and epsf macro

Systematic Study of Electron Localization in an Amorphous Semiconductor

We investigate the electronic structure of gap and band tail states in amorphous silicon. Starting with two 216-atom models of amorphous silicon with defect concentration close to the experiments, we systematically study the dependence of electron localization on basis set, density functional and spin polarization using the first principles density functional code Siesta. We briefly compare three different schemes for characterizing localization: information entropy, inverse participation ratio and spatial variance. Our results show that to accurately describe defect structures within self consistent density functional theory, a rich basis set is necessary. Our study revealed that the localization of the wave function associated with the defect states decreases with larger basis sets and there is some enhancement of localization from GGA relative to LDA. Spin localization results obtained via LSDA calculations, are in reasonable agreement with experiment and with previous LSDA calculations on a-Si:H models.Comment: 16 pages, 11 Postscript figures, To appear in Phys. Rev.