Toward transferable interatomic van der Waals interactions without electrons: The role of multipole electrostatics and many-body dispersion

We estimate polarizabilities of atoms in molecules without electron density, using a Voronoi tesselation approach instead of conventional density partitioning schemes. The resulting atomic dispersion coefficients are calculated, as well as many-body dispersion effects on intermolecular potential energies. We also estimate contributions from multipole electrostatics and compare them to dispersion. We assess the performance of the resulting intermolecular interaction model from dispersion and electrostatics for more than 1,300 neutral and charged, small organic molecular dimers. Applications to water clusters, the benzene crystal, the anti-cancer drug ellipticine---intercalated between two Watson-Crick DNA base pairs, as well as six macro-molecular host-guest complexes highlight the potential of this method and help to identify points of future improvement. The mean absolute error made by the combination of static electrostatics with many-body dispersion reduces at larger distances, while it plateaus for two-body dispersion, in conflict with the common assumption that the simple $1/R^6$ correction will yield proper dissociative tails. Overall, the method achieves an accuracy well within conventional molecular force fields while exhibiting a simple parametrization protocol.Comment: 13 pages, 8 figure

Fractional Shot Noise in the Kondo Regime

Low temperature transport through a quantum dot in the Kondo regime proceeds by a universal combination of elastic and inelastic processes, as dictated by the low-energy Fermi-liquid fixed point. We show that as a result of inelastic processes, the charge detected by a shot-noise experiment is enhanced relative to the noninteracting situation to a universal fractional value, $e^*=5/3 e$. Thus, shot noise reveals that the Kondo effect involves many-body features even at low energies, despite its Fermi-liquid nature. We discuss the influence of symmetry breaking perturbations.Comment: 4 pages, 2 figure

Thermopower of Single-Molecule Devices

We investigate the thermopower of single molecules weakly coupled to metallic leads. We model the molecule in terms of the relevant electronic orbitals coupled to phonons corresponding to both internal vibrations and to oscillations of the molecule as a whole. The thermopower is computed by means of rate equations including both sequential-tunneling and cotunneling processes. Under certain conditions, the thermopower allows one to access the electronic and phononic excitation spectrum of the molecule in a linear-response measurement. In particular, we find that the phonon features are more pronounced for weak lead-molecule coupling. This way of measuring the excitation spectrum is less invasive than the more conventional current-voltage characteristic, which, by contrast, probes the system far from equilibrium.Comment: 13 pages, 7 figures included; minor changes, version published in PR

Theory of the Franck-Condon blockade regime

Strong coupling of electronic and vibrational degrees of freedom entails a low-bias suppression of the current through single-molecule devices, termed Franck-Condon blockade. In the limit of slow vibrational relaxation, transport in the Franck-Condon-blockade regime proceeds via avalanches of large numbers of electrons, which are interrupted by long waiting times without electron transfer. The avalanches consist of smaller avalanches, leading to a self-similar hierarchy which terminates once the number of transferred electrons per avalanche becomes of the order of unity. Experimental signatures of self-similar avalanche transport are strongly enhanced current (shot) noise, as expressed by giant Fano factors, and a power-law noise spectrum. We develop a theory of the Franck-Condon-blockade regime with particular emphasis on effects of electron cotunneling through highly excited vibrational states. As opposed to the exponential suppression of sequential tunneling rates for low-lying vibrational states, cotunneling rates suffer only a power-law suppression. This leads to a regime where cotunneling dominates the current for any gate voltage. Including cotunneling within a rate-equation approach to transport, we find that both the Franck-Condon blockade and self-similar avalanche transport remain intact in this regime. We predict that cotunneling leads to absorption-induced vibrational sidebands in the Coulomb-blockaded regime as well as intrinsic telegraph noise near the charge degeneracy point.Comment: 20 pages, 10 figures; minor changes, version published in Phys. Rev.

Precision of Quantization of the Hall Conductivity in a Sample of Finite Size: Power Law

A microscopic calculation of the conductivity in the integer quantum Hall effect (IQHE) regime is carried out. The problem of precision of quantization is analyzed for samples of finite size. It is demonstrated that the precision of quantization shows a power-law dependence on the sample size. A new scaling parameter describing a dependence of this kind is introduced. It is also demonstrated that the precision of quantization linearly depends on the ratio between the amplitude of the chaotic potential and the cyclotron energy. The results obtained are compared with the magnetotransport measurements in mesoscopic samples.Comment: 5 pages, 4 figure

Constant Size Molecular Descriptors For Use With Machine Learning

A set of molecular descriptors whose length is independent of molecular size is developed for machine learning models that target thermodynamic and electronic properties of molecules. These features are evaluated by monitoring performance of kernel ridge regression models on well-studied data sets of small organic molecules. The features include connectivity counts, which require only the bonding pattern of the molecule, and encoded distances, which summarize distances between both bonded and non-bonded atoms and so require the full molecular geometry. In addition to having constant size, these features summarize information regarding the local environment of atoms and bonds, such that models can take advantage of similarities resulting from the presence of similar chemical fragments across molecules. Combining these two types of features leads to models whose performance is comparable to or better than the current state of the art. The features introduced here have the advantage of leading to models that may be trained on smaller molecules and then used successfully on larger molecules.Comment: 18 pages, 5 figure

Optical excitations in organic molecules, clusters and defects studied by first-principles Green's function methods

Spectroscopic and optical properties of nanosystems and point defects are discussed within the framework of Green's function methods. We use an approach based on evaluating the self-energy in the so-called GW approximation and solving the Bethe-Salpeter equation in the space of single-particle transitions. Plasmon-pole models or numerical energy integration, which have been used in most of the previous GW calculations, are not used. Fourier transforms of the dielectric function are also avoided. This approach is applied to benzene, naphthalene, passivated silicon clusters (containing more than one hundred atoms), and the F center in LiCl. In the latter, excitonic effects and the $1s \to 2p$ defect line are identified in the energy-resolved dielectric function. We also compare optical spectra obtained by solving the Bethe-Salpeter equation and by using time-dependent density functional theory in the local, adiabatic approximation. From this comparison, we conclude that both methods give similar predictions for optical excitations in benzene and naphthalene, but they differ in the spectra of small silicon clusters. As cluster size increases, both methods predict very low cross section for photoabsorption in the optical and near ultra-violet ranges. For the larger clusters, the computed cross section shows a slow increase as function of photon frequency. Ionization potentials and electron affinities of molecules and clusters are also calculated.Comment: 9 figures, 5 tables, to appear in Phys. Rev. B, 200

Size of Fireballs Created in High Energy Lead-Lead Collisions as Inferred from Coulomb Distortions of Pion Spectra

We compute the Coulomb effects produced by an expanding, highly charged fireball on the momentum distribution of pions. We compare our results to data on Au+Au at 11.6 A GeV from E866 at the BNL AGS and to data on Pb+Pb at 158 A GeV from NA44 at the CERN SPS. We conclude that the distortion of the spectra at low transverse momentum and mid-rapidity can be explained in both experiments by the effect of the large amount of participating charge in the central rapidity region. By adjusting the fireball expansion velocity to match the average transverse momentum of protons, we find a best fit when the fireball radius is about 10 fm, as determined by the moment when the pions undergo their last scattering. This value is common to both the AGS and CERN experiments.Comment: Enlarged discussion, new references added, includes new analysis of pi-/pi+ at AGS energies. 12 pages 5 figures, uses LaTex and epsfi