19,165 research outputs found
Homogeneous SPC/E water nucleation in large molecular dynamics simulations
We perform direct large molecular dynamics simulations of homogeneous SPC/E
water nucleation, using up to molecules. Our large system
sizes allow us to measure extremely low and accurate nucleation rates, down to
, helping close the gap between
experimentally measured rates .
We are also able to precisely measure size distributions, sticking
efficiencies, cluster temperatures, and cluster internal densities. We
introduce a new functional form to implement the Yasuoka-Matsumoto nucleation
rate measurement technique (threshold method). Comparison to nucleation models
shows that classical nucleation theory over-estimates nucleation rates by a few
orders of magnitude. The semi-phenomenological nucleation model does better,
under-predicting rates by at worst, a factor of 24. Unlike what has been
observed in Lennard-Jones simulations, post-critical clusters have temperatures
consistent with the run average temperature. Also, we observe that
post-critical clusters have densities very slightly higher, , than
bulk liquid. We re-calibrate a Hale-type vs. scaling relation using
both experimental and simulation data, finding remarkable consistency in over
orders of magnitude in the nucleation rate range, and K in the
temperature range.Comment: Accepted for publication in the Journal of Chemical Physic
Prediction of the Size Distributions of Methanol-Ethanol Clusters Detected in VUV Laser/Time-of-flight Mass Spectrometry
The size distributions and geometries of vapor clusters equilibrated with methanol−ethanol (Me−Et) liquid mixtures were recently studied by vacuum ultraviolet (VUV) laser time-of-flight (TOF) mass spectrometry and density functional theory (DFT) calculations (Liu, Y.; Consta, S.; Ogeer, F.; Shi, Y. J.; Lipson, R. H. Can. J. Chem. 2007, 85, 843−852). On the basis of the mass spectra recorded, it was concluded that the formation of neutral tetramers is particularly prominent. Here we develop grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) frameworks to compute cluster size distributions in vapor mixtures that allow a direct comparison with experimental mass spectra. Using the all-atom optimized potential for liquid simulations (OPLS-AA) force field, we systematically examined the neutral cluster size distributions as functions of pressure and temperature. These neutral cluster distributions were then used to derive ionized cluster distributions to compare directly with the experiments. The simulations suggest that supersaturation at 12 to 16 times the equilibrium vapor pressure at 298 K or supercooling at temperature 240 to 260 K at the equilibrium vapor pressure can lead to the relatively abundant tetramer population observed in the experiments. Our simulations capture the most distinct features observed in the experimental TOF mass spectra: Et3H+ at m/z = 139 in the vapor corresponding to 10:90% Me−Et liquid mixture and Me3H+ at m/z = 97 in the vapors corresponding to 50:50% and 90:10% Me−Et liquid mixtures. The hybrid GCMC scheme developed in this work extends the capability of studying the size distributions of neat clusters to mixed species and provides a useful tool for studying environmentally important systems such as atmospheric aerosols
Segue Between Favorable and Unfavorable Solvation
Solvation of small and large clusters are studied by simulation, considering
a range of solvent-solute attractive energy strengths. Over a wide range of
conditions, both for solvation in the Lennard-Jones liquid and in the SPC model
of water, it is shown that the mean solvent density varies linearly with
changes in solvent-solute adhesion or attractive energy strength. This behavior
is understood from the perspective of Weeks' theory of solvation [Ann. Rev.
Phys. Chem. 2002, 53, 533] and supports theories based upon that perspective.Comment: 8 pages, 7 figure
On the transferability of three water models developed by adaptive force matching
Water is perhaps the most simulated liquid. Recently three water models have
been developed following the adaptive force matching (AFM) method that provides
excellent predictions of water properties with only electronic structure
information as a reference. Compared to many other electronic structure based
force fields that rely on fairly sophisticated energy expressions, the AFM
water models use point-charge based energy expressions that are supported by
most popular molecular dynamics packages. An outstanding question regarding
simple force fields is whether such force fields provide reasonable
transferability outside of their conditions of parameterization. A survey of
three AFM water models, B3LYPD-4F, BLYPSP-4F, and WAIL are provided for
simulations under conditions ranging from the melting point up to the critical
point. By including ice-Ih configurations in the training set, the WAIL
potential predicts the melting temperate, TM, of ice-Ih correctly. Without
training for ice, BLYPSP-4F underestimates TM by about 15 K. Interestingly, the
B3LYPD-4F model gives a TM 14 K too high. The overestimation of TM by B3LYPD-4F
mostly likely reflects a deficiency of the B3LYP reference. The BLYPSP-4F model
gives the best estimate of the boiling temperature TB and is arguably the best
potential for simulating water in the temperature range from TM to TB. None of
the three AFM potentials provides a good description of the critical point.
Although the B3LYPD-4F model gives the correct critical temperature TC and
critical density, there are good reasons to believe the agreement is reached
fortuitously. Links to Gromacs input files for the three water models are
provided at the end of the paper.Comment: 25 pages, 2 figure
Nonisothermal homogeneous nucleation
Classical homogeneous nucleation theory is extended to nonisothermal conditions through simultaneous cluster mass and energy balances. The transient nucleation of water vapor following a sudden increase in saturation ratio is studied by numerically solving the coupled mass and energy balance equations. The ultimate steady state nucleation rate, considering nonisothermal effects, is found to be lower than the corresponding isothermal rate, with the discrepancy increasing as the pressure of the background gas decreases. After the decay of the initial temperature transients, subcritical clusters in the vicinity of the critical cluster are found to have temperatures elevated with respect to that of the background gas
Binary nucleation of sulfuric acid-water: Monte Carlo simulation
We have developed a classical mechanical model for the H2SO4/H2O binary system. Monte Carlo simulation was performed in a mixed ensemble, in which the number of sulfuric acid molecules is fixed while that of water molecules is allowed to fluctuate. Simulation in this ensemble is computationally efficient compared to conventional canonical simulation, both in sampling very different configurations of clusters relevant in nucleation and in evaluating the free energy of cluster formation. The simulation yields molecular level information, such as the shape of the clusters and the dissociation behavior of the acid molecule in the cluster. Our results indicate that the clusters are highly nonspherical as a result of the anisotropic intermolecular interactions and that a cluster with a given number of acid molecules has several very different conformations, which are close in free energy and hence equally relevant in nucleation. The dissociation behavior of H2SO4 in a cluster differs markedly from that in bulk solution and depends sensitively on the assumed value of the free energy f(hb) of the dissociation reaction H2SO4+H2O-HSO4-. H3O+. In a small cluster, no dissociation is observed. As the cluster size becomes larger, the probability of having an HSO4-. H3O+ ion pair increases. However, in clusters relevant in nucleation, the resulting ion pairs remain in contact; about 240 water molecules are required to observe behavior that resembles that in bulk solution. If a larger value of f(hb) is assumed to reflect its uncertainty, the probability of dissociation becomes negligible. A reversible work surface obtained for a condition typical of vapor to liquid nucleation suggests that the rate-limiting step of new particle formation is a binary collision of two hydrated sulfuric acid molecules. The ion pairs formed by dissociation play a key role in stabilizing the resulting cluster. The reversible work surface is sensitive to the assumed value of f(hb), thus pointing to the need for an accurate estimate of the quantity either by ab initio calculations or experiments
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