3,603 research outputs found
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 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, .
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 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
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