412 research outputs found
Towards First-principles Electrochemistry
Chemisorbed molecules at a fuel cell electrode are a very sensitive probe of
the surrounding electrochemical environment, and one that can be accurately
monitored with different spectroscopic techniques. We develop a comprehensive
electrochemical model to study molecular chemisorption at either constant
charge or fixed applied voltage, and calculate from first principles the
voltage dependence of vibrational frequencies -- the vibrational Stark effect
-- for CO adsorbed on close-packed platinum electrodes. The predicted
vibrational Stark slopes are found to be in very good agreement with
experimental electrochemical spectroscopy data, thereby resolving previous
controversies in the quantitative interpretation of in-situ experiments and
elucidating the relation between canonical and grand-canonicaldescriptions of
vibrational surface phenomena.Comment: 10 pages, 2 figure
Nonlinear instability of density-independent orbital-free kinetic energy functionals
We study in this article the mathematical properties of a class of
orbital-free kinetic energy functionals. We prove that these models are
linearly stable but nonlinearly unstable, in the sense that the corresponding
kinetic energy functionals are not bounded from below. As a matter of
illustration, we provide an example of an electronic density of simple shape
the kinetic energy of which is negative.Comment: 14 pages, 1 figur
Non-perturbative embedding of local defects in crystalline materials
We present a new variational model for computing the electronic first-order
density matrix of a crystalline material in presence of a local defect. A
natural way to obtain variational discretizations of this model is to expand
the difference Q between the density matrix of the defective crystal and the
density matrix of the perfect crystal, in a basis of precomputed maximally
localized Wannier functions of the reference perfect crystal. This approach can
be used within any semi-empirical or Density Functional Theory framework.Comment: 13 pages, 4 figure
Perspective: Polarizable continuum models for quantum-mechanical descriptions
Polarizable continuum solvation models are nowadays the most popular approach to describe solvent effects in the context of quantum mechanical calculations. Unexpectedly, despite their widespread use in all branches of quantum chemistry and beyond, important aspects of both their theoretical formulation and numerical implementation are still not completely understood. In particular, in this perspective we focus on the numerical issues of their implementation when applied to large systems and on the theoretical framework needed to treat time dependent problems and excited states or to deal with electronic correlation. Possible extensions beyond a purely electrostatic model and generalizations to environments beyond common solvents are also critically presented and discussed. Finally, some possible new theoretical approaches and numerical strategies are suggested to overcome the obstacles which still prevent a full exploitation of these models
Unique Solutions to Hartree-Fock Equations for Closed Shell Atoms
In this paper we study the problem of uniqueness of solutions to the Hartree
and Hartree-Fock equations of atoms. We show, for example, that the
Hartree-Fock ground state of a closed shell atom is unique provided the atomic
number is sufficiently large compared to the number of electrons. More
specifically, a two-electron atom with atomic number has a unique
Hartree-Fock ground state given by two orbitals with opposite spins and
identical spatial wave functions. This statement is wrong for some , which
exhibits a phase segregation.Comment: 18 page
Spectral method for the time-dependent Gross-Pitaevskii equation with a harmonic trap
We study the numerical resolution of the time-dependent Gross-Pitaevskii
equation, a non-linear Schroedinger equation used to simulate the dynamics of
Bose-Einstein condensates. Considering condensates trapped in harmonic
potentials, we present an efficient algorithm by making use of a spectral
Galerkin method, using a basis set of harmonic oscillator functions, and the
Gauss-Hermite quadrature. We apply this algorithm to the simulation of
condensate breathing and scissors modes.Comment: 23 pages, 5 figure
Renormalization and asymptotic expansion of Dirac's polarized vacuum
We perform rigorously the charge renormalization of the so-called reduced
Bogoliubov-Dirac-Fock (rBDF) model. This nonlinear theory, based on the Dirac
operator, describes atoms and molecules while taking into account vacuum
polarization effects. We consider the total physical density including both the
external density of a nucleus and the self-consistent polarization of the Dirac
sea, but no `real' electron. We show that it admits an asymptotic expansion to
any order in powers of the physical coupling constant \alphaph, provided that
the ultraviolet cut-off behaves as \Lambda\sim e^{3\pi(1-Z_3)/2\alphaph}\gg1.
The renormalization parameter $
A theory of -dissipative solvers for scalar conservation laws with discontinuous flux
We propose a general framework for the study of contractive semigroups
of solutions to conservation laws with discontinuous flux. Developing the ideas
of a number of preceding works we claim that the whole admissibility issue is
reduced to the selection of a family of "elementary solutions", which are
certain piecewise constant stationary weak solutions. We refer to such a family
as a "germ". It is well known that (CL) admits many different contractive
semigroups, some of which reflects different physical applications. We revisit
a number of the existing admissibility (or entropy) conditions and identify the
germs that underly these conditions. We devote specific attention to the
anishing viscosity" germ, which is a way to express the "-condition" of
Diehl. For any given germ, we formulate "germ-based" admissibility conditions
in the form of a trace condition on the flux discontinuity line (in the
spirit of Vol'pert) and in the form of a family of global entropy inequalities
(following Kruzhkov and Carrillo). We characterize those germs that lead to the
-contraction property for the associated admissible solutions. Our
approach offers a streamlined and unifying perspective on many of the known
entropy conditions, making it possible to recover earlier uniqueness results
under weaker conditions than before, and to provide new results for other less
studied problems. Several strategies for proving the existence of admissible
solutions are discussed, and existence results are given for fluxes satisfying
some additional conditions. These are based on convergence results either for
the vanishing viscosity method (with standard viscosity or with specific
viscosities "adapted" to the choice of a germ), or for specific germ-adapted
finite volume schemes
A new approach to the modelling of local defects in crystals: the reduced Hartree-Fock case
This article is concerned with the derivation and the mathematical study of a
new mean-field model for the description of interacting electrons in crystals
with local defects. We work with a reduced Hartree-Fock model, obtained from
the usual Hartree-Fock model by neglecting the exchange term. First, we recall
the definition of the self-consistent Fermi sea of the perfect crystal, which
is obtained as a minimizer of some periodic problem, as was shown by Catto, Le
Bris and Lions. We also prove some of its properties which were not mentioned
before. Then, we define and study in details a nonlinear model for the
electrons of the crystal in the presence of a defect. We use formal analogies
between the Fermi sea of a perturbed crystal and the Dirac sea in Quantum
Electrodynamics in the presence of an external electrostatic field. The latter
was recently studied by Hainzl, Lewin, S\'er\'e and Solovej, based on ideas
from Chaix and Iracane. This enables us to define the ground state of the
self-consistent Fermi sea in the presence of a defect. We end the paper by
proving that our model is in fact the thermodynamic limit of the so-called
supercell model, widely used in numerical simulations.Comment: Final version, to appear in Comm. Math. Phy
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