83 research outputs found
Real single ion solvation free energies with quantum mechanical simulation
Single ion solvation free energies are one of the most important properties
of electrolyte solutions and yet there is ongoing debate about what these
values are. Only the values for neutral ion pairs are known. Here, we use DFT
interaction potentials with molecular dynamics simulation (DFT-MD) combined
with a modified version of the quasi-chemical theory (QCT) to calculate these
energies for the lithium and fluoride ions. A method to correct for the error
in the DFT functional is developed and very good agreement with the
experimental value for the lithium fluoride pair is obtained. Moreover, this
method partitions the energies into physically intuitive terms such as surface
potential, cavity and charging energies which are amenable to descriptions with
reduced models. Our research suggests that lithium's solvation free energy is
dominated by the free energetics of a charged hard sphere, whereas fluoride
exhibits significant quantum mechanical behavior that cannot be simply
described with a reduced model.Comment: 13 pages, 4 figure
Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions
Determining the solvation free energies of single ions in water is one of the
most fundamental problems in physical chemistry and yet many unresolved
questions remain. In particular, the ability to decompose the solvation free
energy into simple and intuitive contributions will have important implications
for models of electrolyte solution. Here, we provide definitions of the various
types of single ion solvation free energies based on different simulation
protocols. We calculate solvation free energies of charged hard spheres using
density functional theory interaction potentials with molecular dynamics
simulation (DFT-MD) and isolate the effects of charge and cavitation, comparing
to the Born (linear response) model. We show that using uncorrected Ewald
summation leads to unphysical values for the single ion solvation free energy
and that charging free energies for cations are approximately linear as a
function of charge but that there is a small non-linearity for small anions.
The charge hydration asymmetry (CHA) for hard spheres, determined with quantum
mechanics, is much larger than for the analogous real ions. This suggests that
real ions, particularly anions, are significantly more complex than simple
charged hard spheres, a commonly employed representation.Comment: 28 pages, 5 figure
Smoothed Dissipative Particle Dynamics model for mesoscopic multiphase flows in the presence of thermal fluctuations
Thermal fluctuations cause perturbations of fluid-fluid interfaces and highly
nonlinear hydrodynamics in multiphase flows. In this work, we develop a novel
multiphase smoothed dissipative particle dynamics model. This model accounts
for both bulk hydrodynamics and interfacial fluctuations. Interfacial surface
tension is modeled by imposing a pairwise force between SDPD particles. We show
that the relationship between the model parameters and surface tension,
previously derived under the assumption of zero thermal fluctuation, is
accurate for fluid systems at low temperature but overestimates the surface
tension for intermediate and large thermal fluctuations. To analyze the effect
of thermal fluctuations on surface tension, we construct a coarse-grained Euler
lattice model based on the mean field theory and derive a semi-analytical
formula to directly relate the surface tension to model parameters for a wide
range of temperatures and model resolutions. We demonstrate that the present
method correctly models the dynamic processes, such as bubble coalescence and
capillary spectra across the interface
Mass Density Fluctuations in Quantum and Classical descriptions of Liquid Water
First principles molecular dynamics simulation protocol is established using
revised functional of Perdew-Burke-Ernzerhof (revPBE) in conjunction with
Grimme's third generation of dispersion (D3) correction to describe properties
of water at ambient conditions. This study also demonstrates the consistency of
the structure of water across both isobaric (NpT) and isothermal (NVT)
ensembles. Going beyond the standard structural benchmarks for liquid water, we
compute properties that are connected to both local structure and mass density
uctuations that are related to concepts of solvation and hydrophobicity. We
directly compare our revPBE results to the Becke-Lee-Yang-Parr (BLYP) plus
Grimme dispersion corrections (D2) and both the empirical fixed charged model
(SPC/E) and many body interaction potential model (MB-pol) to further our
understanding of how the computed properties herein depend on the form of the
interaction potential
Variational Transition State Theory Evaluation Of The Rate Constant For Proton Transfer In A Polar Solvent
Variational transition state theory (VTST) is used to calculate rate constants for a model proton transfer reaction in a polar solvent. We start from an explicit description of the reacting solute in a solvent, and we model the effects of solvation on the reaction dynamics by a generalized Langevin equation (GLE) for the solute. In this description, the effects of solvation on the reaction energetics are included in the potential of mean force, and dynamical, or nonequilibrium, solvation is included by solvent friction. The GLE solvation dynamics are approximated by a collection of harmonic oscillators that are linearly coupled to the coordinates of the reacting system. This approach is applied to a model developed by Azzouz and Borgis [J. Chem. Phys. 98, 7361 (1993)] to represent proton transfer in a phenol-amine complex in liquid methyl chloride. In particular, semiclassical VTST, including multidimensional tunneling contributions, is applied to this model with three explicit solute coordinates and a multioscillator GLE description of solvation to calculate rate constants. We compare our computed rate constants and H/D kinetic isotope effects to previous calculations using other approximate dynamical theories, including approaches based on one-dimensional models, molecular dynamics with quantum transitions, and path integrals. By examining a systematic sequence of 18 different sets of approximations, we clarify some of the factors (such as classical vibrations, harmonic approximations, quantum character of reaction-coordinate motion, and nonequilibrium solvation) that contribute to the different predictions of various approximation schemes in the literature. (C) 2001 American Institute of Physics
Optical assembly of nanostructures mediated by surface roughness
Rigorous understanding of the self-assembly of colloidal nanocrystals is
crucial to the development of tailored nanostructured materials. Despite
extensive studies, a mechanistic understanding of self-assembly under
non-equilibrium driven by an external field remains an ongoing challenge. We
demonstrate self-assembly by optical tweezers imposing an external attractive
field for cubic-phase sodium yttrium fluoride nanocrystals. We show that
surface roughness of the nanocrystals is a decisive factor for contact leading
to assembly between the nanocrystals, manifested by the roughness-dependent
hydrodynamic resistivity. This provides direct evidence that dynamics are
equally important to energetics in understanding self-assembly. These results
have implications in a wide variety of different fields, such as in
understanding the factors that mediate oriented attachment-based crystal growth
or in interpreting the structure of binding sites on viruses.Comment: 21 pages, 3 main figures, 8 supplemental figures, 2 supplemental
videos. Submitted to Physical Review Letter
Potential quantum advantage for simulation of fluid dynamics
Numerical simulation of turbulent fluid dynamics needs to either parameterize
turbulence-which introduces large uncertainties-or explicitly resolve the
smallest scales-which is prohibitively expensive. Here we provide evidence
through analytic bounds and numerical studies that a potential quantum
exponential speedup can be achieved to simulate the Navier-Stokes equations
governing turbulence using quantum computing. Specifically, we provide a
formulation of the lattice Boltzmann equation for which we give evidence that
low-order Carleman linearization is much more accurate than previously believed
for these systems and that for computationally interesting examples. This is
achieved via a combination of reformulating the nonlinearity and accurately
linearizing the dynamical equations, effectively trading nonlinearity for
additional degrees of freedom that add negligible expense in the quantum
solver. Based on this we apply a quantum algorithm for simulating the
Carleman-linerized lattice Boltzmann equation and provide evidence that its
cost scales logarithmically with system size, compared to polynomial scaling in
the best known classical algorithms. This work suggests that an exponential
quantum advantage may exist for simulating fluid dynamics, paving the way for
simulating nonlinear multiscale transport phenomena in a wide range of
disciplines using quantum computing
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