6,726 research outputs found
Development of an Advanced Force Field for Water using Variational Energy Decomposition Analysis
Given the piecewise approach to modeling intermolecular interactions for
force fields, they can be difficult to parameterize since they are fit to data
like total energies that only indirectly connect to their separable functional
forms. Furthermore, by neglecting certain types of molecular interactions such
as charge penetration and charge transfer, most classical force fields must
rely on, but do not always demonstrate, how cancellation of errors occurs among
the remaining molecular interactions accounted for such as exchange repulsion,
electrostatics, and polarization. In this work we present the first generation
of the (many-body) MB-UCB force field that explicitly accounts for the
decomposed molecular interactions commensurate with a variational energy
decomposition analysis, including charge transfer, with force field design
choices that reduce the computational expense of the MB-UCB potential while
remaining accurate. We optimize parameters using only single water molecule and
water cluster data up through pentamers, with no fitting to condensed phase
data, and we demonstrate that high accuracy is maintained when the force field
is subsequently validated against conformational energies of larger water
cluster data sets, radial distribution functions of the liquid phase, and the
temperature dependence of thermodynamic and transport water properties. We
conclude that MB-UCB is comparable in performance to MB-Pol, but is less
expensive and more transferable by eliminating the need to represent
short-ranged interactions through large parameter fits to high order
polynomials
X-ray Diffraction and Molecular Dynamics Study of Medium-range Order in Ambient and Hot Water
We have developed x-ray diffraction measurements with high energy-resolution
and accuracy to study water structure at three different temperatures (7, 25
and 66 C) under normal pressure. Using a spherically curved Ge crystal an
energy resolution better than 15 eV has been achieved which eliminates
influence from Compton scattering. The high quality of the data allows a
precise oxygen-oxygen pair correlation function (PCF) to be directly derived
from the Fourier transform of the experimental data resolving shell structure
out to ~12 {\AA}, i.e. 5 hydration shells. Large-scale molecular dynamics (MD)
simulations using the TIP4P/2005 force-field reproduce excellently the
experimental shell-structure in the range 4-12 {\AA} although less agreement is
seen for the first peak in the PCF. The Local Structure Index [J. Chem. Phys.
104, 7671 (1996)] identifies a tetrahedral minority giving the
intermediate-range oscillations in the PCF and a disordered majority providing
a more featureless background in this range. The current study supports the
proposal that the structure of liquid water, even at high temperatures, can be
described in terms of a two-state fluctuation model involving local structures
related to the high-density and low-density forms of liquid water postulated in
the liquid-liquid phase transition hypothesis.Comment: Submitted to Phys. Chem. Chem. Phy
Recommended from our members
Hydrogen bonding structure of confined water templated by a metal-organic framework with open metal sites.
Water in confinement exhibits properties significantly different from bulk water due to frustration in the hydrogen-bond network induced by interactions with the substrate. Here, we combine infrared spectroscopy and many-body molecular dynamics simulations to probe the structure and dynamics of confined water as a function of relative humidity within a metal-organic framework containing cylindrical pores lined with ordered cobalt open coordination sites. Building upon the agreement between experimental and theoretical spectra, we demonstrate that water at low relative humidity binds initially to open metal sites and subsequently forms disconnected one-dimensional chains of hydrogen-bonded water molecules bridging between cobalt atoms. With increasing relative humidity, these water chains nucleate pore filling, and water molecules occupy the entire pore interior before the relative humidity reaches 30%. Systematic analysis of rotational and translational dynamics indicates heterogeneity in this pore-confined water, with water molecules displaying variable mobility as a function of distance from the interface
Exploration of aqueous interfaces and their effect on ion behavior
An in-depth understanding of a wide range of physical, chemical, atmospheric and biological processes can only be achieved after the structure and dynamics of interfaces and the interfacial behavior of aqueous species, such as ions, are thoroughly studied and understood. This dissertation describes computational studies conducted to gain a more comprehensive understanding of such interfaces and the behavior of ions in the bulk and interfacial regions of the (1) air/water interface, and (2) alkane/water interfaces.
At the air/water interface the effect of counterion (sodium cations) charge and the influence of ion pairing on anion (chloride) propensity for the air/water interface of water was investigated. Higher counterion charge led to greater interfacial activity of the chloride anions and also caused stronger binding between the sodium and chloride ions. Shorter sodium-chloride interatomic distance also led to greater anion interfacial propensity while dampening the interaction strength between the counterion and anion had a small effect on propensity of the anions for the interface. Another phenomenon examined at the air/water interface was the effect of the halide ion in various sodium halide electrolyte solutions on the surface tension and surface excess while including electrostatic damping in the simulation model. Divalent strontium chloride was also examined in comparison to monovalent sodium chloride. Findings suggested that the smaller halide ions were found farthest from the air/water interface—in keeping with trends from previous studies—and resulted in the largest (most negative) surface excess, which would in turn cause the greatest increase in surface tension of water. Divalent strontium chloride had a more negative surface excess when compared to sodium chloride and the inclusion of electrostatic damping in the models reduced propensity of the ions for the interface and caused overall increase in surface excess.
The alkane/water interface was investigated to determine the effect of changing the length of the alkyl chain on the water/alkane interfacial width. Two separate studies found that longer alkane chain length led to shorter alkane/water interfacial widths. A long term goal of this research is to catalog the behavior of ionic species at different interfaces. The distribution of sodium-halide ions was compared at the alkane/water and air/water interfaces. Sodium halide ions were found closer to the air/water interface than the alkane/water interface. In the future, similar studies will be carried out at the alcohol/water interface and the effects of the nature of the organic phase (alkane or alcohol with varied chain lengths, degrees of branching, and solubility in water) will be examined
Thermodynamics, Structure, and Dynamics of Water Confined between Hydrophobic Plates
We perform molecular dynamics simulations of 512 water-like molecules that
interact via the TIP5P potential and are confined between two smooth
hydrophobic plates that are separated by 1.10 nm. We find that the anomalous
thermodynamic properties of water are shifted to lower temperatures relative to
the bulk by K. The dynamics and structure of the confined water
resemble bulk water at higher temperatures, consistent with the shift of
thermodynamic anomalies to lower temperature. Due to this shift, our
confined water simulations (down to K) do not reach sufficiently low
temperature to observe a liquid-liquid phase transition found for bulk water at
K using the TIP5P potential. We find that the different
crystalline structures that can form for two different separations of the
plates, 0.7 nm and 1.10 nm, have no counterparts in the bulk system, and
discuss the relevance to experiments on confined water.Comment: 31 pages, 14 figure
- …