Vibrational Density Matrix Renormalization Group

Variational approaches for the calculation of vibrational wave functions and energies are a natural route to obtain highly accurate results with controllable errors. However, the unfavorable scaling and the resulting high computational cost of standard variational approaches limit their application to small molecules with only few vibrational modes. Here, we demonstrate how the density matrix renormalization group (DMRG) can be exploited to optimize vibrational wave functions (vDMRG) expressed as matrix product states. We study the convergence of these calculations with respect to the size of the local basis of each mode, the number of renormalized block states, and the number of DMRG sweeps required. We demonstrate the high accuracy achieved by vDMRG for small molecules that were intensively studied in the literature. We then proceed to show that the complete fingerprint region of the sarcosyn-glycin dipeptide can be calculated with vDMRG.Comment: 21 pages, 5 figures, 4 table

Gaussian-Charge Polarizable Interaction Potential for Carbon Dioxide

A number of simple pair interaction potentials of the carbon dioxide molecule are investigated and found to underestimate the magnitude of the second virial coefficient in the temperature interval 220 K to 448 K by up to 20%. Also the third virial coefficient is underestimated by these models. A rigid, polarizable, three-site interaction potential reproduces the experimental second and third virial coefficients to within a few percent. It is based on the modified Buckingham exp-6 potential, an anisotropic Axilrod-Teller correction and Gaussian charge densities on the atomic sites with an inducible dipole at the center of mass. The electric quadrupole moment, polarizability and bond distances are set to equal experiment. Density of the fluid at 200 and 800 bars pressure is reproduced to within some percent of observation over the temperature range 250 K to 310 K. The dimer structure is in passable agreement with electronically resolved quantum-mechanical calculations in the literature, as are those of the monohydrated monomer and dimer complexes using the polarizable GCPM water potential. Qualitative agreement with experiment is also obtained, when quantum corrections are included, for the relative stability of the trimer conformations, which is not the case for the pair potentials.Comment: Error in the long-range correction fixed and three-body dispersion introduced. 32 pages (incl. title page), 7 figures, 9 tables, double-space

Designing molecules to bypass the singlet-triplet bottleneck in the electroluminescence of organic light-emitting-diode materials

Electroluminescence in organic light emitting diode (OLED) materials occurs via the recombination of excitonic electrons-hole pairs Only the singlet excitons of commonly used OLED materials, e.g., Aluminum trihydroxyquinoline (AlQ$_3$), decay radiatively, limiting the external quantum efficiency to a maximum 25%. Thus 75% of the energy is lost due to the triplet bottleneck for radiative recombination. We consider molecules derived from AlQ$_3$ which bypass the triplet bottleneck by designing structures which contain strong spin-orbit coupling. As a first stage of this work, groundstate energies and vertical excitation energies of Al-arsenoquinolines and Al-boroarsenoquinolines are calculated. It is found that the substitution of N by As leads to very favourable results, while the boron substitution leads to no advantage.Comment: 4 pages, 4 figue

Dust in the Local Interstellar Wind

The gas-to-dust mass ratios found for interstellar dust within the Solar System, versus values determined astronomically for the cloud around the Solar System, suggest that large and small interstellar grains have separate histories, and that large interstellar grains preferentially detected by spacecraft are not formed exclusively by mass exchange with nearby interstellar gas. Observations by the Ulysses and Galileo satellites of the mass spectrum and flux rate of interstellar dust within the heliosphere are combined with information about the density, composition, and relative flow speed and direction of interstellar gas in the cloud surrounding the solar system to derive an in situ value for the gas-to-dust mass ratio, $R_{g/d} = 94^{+46}_{-38}$. Hubble observations of the cloud surrounding the solar system yield a gas-to-dust mass ratio of Rg/d=551+61-251 when B-star reference abundances are assumed. The exclusion of small dust grains from the heliosheath and heliosphere regions are modeled, increasing the discrepancy between interstellar and in situ observations. The shock destruction of interstellar grains is considered, and comparisons are made with interplanetary and presolar dust grains.Comment: 87 pages, 9 figures, 6 tables, accepted for publication in Astrophysical Journal. Uses AASTe

The supercluster--void network III. The correlation function as a geometrical statistic

We investigate properties of the correlation function of clusters of galaxies using geometrical models. On small scales the correlation function depends on the shape and the size of superclusters. On large scales it describes the geometry of the distribution of superclusters. If superclusters are distributed randomly then the correlation function on large scales is featureless. If superclusters and voids have a tendency to form a regular lattice then the correlation function on large scales has quasi-regularly spaced maxima and minima of decaying amplitude; i.e., it is oscillating. The period of oscillations is equal to the step size of the grid of the lattice. We calculate the power spectrum for our models and compare the geometrical information of the correlation function with other statistics. We find that geometric properties (the regularity of the distribution of clusters on large scales) are better quantified by the correlation function. We also analyse errors in the correlation function and the power spectrum by generating random realizations of models and finding the scatter of these realizations.Comment: MNRAS LaTex style, 12 pages, 7 PostScript figures embedded, accepted by MNRA

Steps toward the power spectrum of matter. I.The mean spectrum of galaxies

We calculate the mean power spectrum of galaxies using published power spectra of galaxies and clusters of galaxies. On small scales we use the power spectrum derived from the 2-dimensional distribution of APM galaxies, on large scales we use power spectra derived from 3-dimensional data for galaxy and cluster samples. Spectra are reduced to real space and to the amplitude of the power spectrum of APM galaxies. Available data indicate the presence of two different populations in the nearby Universe. Clusters of galaxies sample a relatively large region in the Universe where rich, medium and poor superclusters are well represented. Their mean power spectrum has a spike on scale 120 h^{-1}Mpc, followed by an approximate power-law spectrum of index n = -1.9 towards small scales. The power spectrum found from LCRS and IRAS 1.2 Jy surveys is flatter around the maximum, which may represent regions of the Universe with medium-rich and poor superclusters.Comment: LaTex (sty files added), 35 pages, 5 PostScript figures and Table with mean power spectrum embedded, Astrophysical Journal (accepted

Turbulent-like fluctuations in quasistatic flow of granular media

We analyze particle velocity fluctuations in a simulated granular system subjected to homogeneous quasistatic shearing. We show that these fluctuations share the following scaling characteristics of fluid turbulence in spite of their different physical origins: 1) Scale-dependent probability distribution with non-Guassian broadening at small time scales; 2) Power-law spectrum, reflecting long-range correlations and the self-affine nature of the fluctuations; 3) Superdiffusion with respect to the mean background flow

Long time correlations in Lagrangian dynamics: a key to intermittency in turbulence

New aspects of turbulence are uncovered if one considers flow motion from the perspective of a fluid particle (known as the Lagrangian approach) rather than in terms of a velocity field (the Eulerian viewpoint). Using a new experimental technique, based on the scattering of ultrasounds, we have obtained a direct measurement of particle velocities, resolved at all scales, in a fully turbulent flow. It enables us to approach intermittency in turbulence from a dynamical point of view and to analyze the Lagrangian velocity fluctuations in the framework of random walks. We find experimentally that the elementary steps in the 'walk' have random uncorrelated directions but a magnitude that is extremely long-range correlated in time. Theoretically, we study a Langevin equation that incorporates these features and we show that the resulting dynamics accounts for the observed one- and two-point statistical properties of the Lagrangian velocity fluctuations. Our approach connects the intermittent statistical nature of turbulence to the dynamics of the flow.Comment: 4 pages, 4 figure

Consequences of a Change in the Galactic Environment of the Sun

The interaction of the heliosphere with interstellar clouds has attracted interest since the late 1920's, both with a view to explaining apparent quasi-periodic climate "catastrophes" as well as periodic mass extinctions. Until recently, however, models describing the solar wind - local interstellar medium (LISM) interaction self-consistently had not been developed. Here, we describe the results of a two-dimensional (2D) simulation of the interaction between the heliosphere and an interstellar cloud with the same properties as currently, except that the neutral H density is increased from the present value of n(H) ~ 0.2 cm^-3 to 10 cm^-3. The mutual interaction of interstellar neutral hydrogen and plasma is included. The heliospheric cavity is reduced considerably in size (approximately 10 - 14 AU to the termination shock in the upstream direction) and is highly dynamical. The interplanetary environment at the orbit of the Earth changes markedly, with the density of interstellar H increasing to ~2 cm^-3. The termination shock itself experiences periods where it disappears, reforms and disappears again. Considerable mixing of the shocked solar wind and LISM occurs due to Rayleigh-Taylor-like instabilities at the nose, driven by ion-neutral friction. Implications for two anomalously high concentrations of 10Be found in Antarctic ice cores 33 kya and 60 kya, and the absence of prior similar events, are discussed in terms of density enhancements in the surrounding interstellar cloud. The calculation presented here supports past speculation that the galactic environment of the Sun moderates the interplanetary environment at the orbit of the Earth, and possibly also the terrestrial climate.Comment: 23 pages, 2 color plates (jpg), 3 figures (eps