88,145 research outputs found
Electrostatic Point Charge Fitting as an Inverse Problem: Revealing the Underlying Ill-Conditioning
Atom-centered point charge model of the molecular electrostatics---a major
workhorse of the atomistic biomolecular simulations---is usually parameterized
by least-squares (LS) fitting of the point charge values to a reference
electrostatic potential, a procedure that suffers from numerical instabilities
due to the ill-conditioned nature of the LS problem. Here, to reveal the
origins of this ill-conditioning, we start with a general treatment of the
point charge fitting problem as an inverse problem, and construct an
analytically soluble model with the point charges spherically arranged
according to Lebedev quadrature naturally suited for the inverse electrostatic
problem. This analytical model is contrasted to the atom-centered point-charge
model that can be viewed as an irregular quadrature poorly suited for the
problem. This analysis shows that the numerical problems of the point charge
fitting are due to the decay of the curvatures corresponding to the
eigenvectors of LS sum Hessian matrix. In part, this ill-conditioning is
intrinsic to the problem and related to decreasing electrostatic contribution
of the higher multipole moments, that are, in the case of Lebedev grid model,
directly associated with the Hessian eigenvectors. For the atom-centered model,
this association breaks down beyond the first few eigenvectors related to the
high-curvature monopole and dipole terms; this leads to even wider spread-out
of the Hessian curvature values. Using these insights, it is possible to
alleviate the ill-conditioning of the LS point-charge fitting without
introducing external restraints and/or constraints. Also, as the analytical
Lebedev grid PC model proposed here can reproduce multipole moments up to a
given rank, it may provide a promising alternative to including explicit
multipole terms in a force field
Macroscopic effects in attosecond pulse generation
We examine how the generation and propagation of high-order harmonics in a
partly ionized gas medium affect their strength and synchronization. The
temporal properties of the resulting attosecond pulses generated in long gas
targets can be significantly influenced by macroscopic effects, in particular
by the intensity in the medium and the degree of ionization. Under some
conditions, the use of gas targets longer than the absorption length can lead
to the generation of self-compressed attosecond pulses. We show this effect
experimentally, using long argon-filled gas cells as generating medium.Comment: 5 pages 4 figure
A New Model of Chemical Bonding in Ionic Melts
We developed a new physical model to predict macroscopic properties of
inorganic molten systems using a realistic description of inter-atomic
interactions. Unlike the conventional approach, which tends to overestimate
viscosity by several times, our systems consist of a set of ions with an
admixture of neutral atoms. The neutral atom subsystem is a consequence of the
covalent/ionic state reduction, occurring in the liquid phase. Comparison of
the calculated macroscopic properties (shear viscosity and self-diffusion
constants) with the experiment demonstrates good performance of our model. The
presented approach is inspired by a significant degree of covalent interaction
between the alkali and chlorine atoms, predicted by the coupled cluster theory
Soft Manifold Dynamics Behind Negative Thermal Expansion
Minimal models are developed to examine the origin of large negative thermal
expansion (NTE) in under-constrained systems. The dynamics of these models
reveals how underconstraint can organize a thermodynamically extensive manifold
of low-energy modes which not only drives NTE but extends across the Brillioun
zone. Mixing of twist and translation in the eigenvectors of these modes, for
which in ZrW2O8 there is evidence from infrared and neutron scattering
measurements, emerges naturally in our model as a signature of the dynamics of
underconstraint.Comment: 5 pages, 3 figure
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