Equilibrium molecular dynamics calculation of the bulk viscosity of liquid water

Twenty independent equilibrium molecular dynamics simulations were performed in NVE ensemble to calculate the bulk viscosity of water at a temperature of 303 K and a density of 0.999 gcm^?3. The energy of each simulation with a production time of 200ps was conserved within 1 part in 10⁴. By stopping the velocity-scaling procedure at a proper step, the energies of independent simulations were specified precisely. This caused the simulations of different start configurations to sample the same NVE ensemble. The shear viscosity of SPC/E water obtained in the present study was 6.5±0.4 × 10^?4 Pas, which is in close agreement with a previous calculation in the NVT ensemble (Balasubramanian, S., Mundy, C. J., and Klein, M. L., 1996, J. clzern. Phys., 105, 11 190). The bulk viscosity was 15.5 ± 1.6 × 10^?4 Pas, which is 27% smaller than the experimental value. Thus, like its behaviour in predicting the shear viscosity, the SPC/E model also underestimates the bulk viscosity of real water.     

Femtosecond solvation and charge transfer dynamics in liquid solution

Time-resolved fluorescence up-conversion experiments have been performed for a few fluorescent organic charge transfer molecules in liquid solution. Dynamic Stokes shifts have been measured, with a time resolution of 150 fs, for the probe molecules in alcoholic and ethereal solvents. The results reveal solvation dynamics determined by “inertial free streaming” motions of the solvent molecules in the solvent cages and rotational diffusion motions of the solvent molecules. Simulations of the temporal changes in the fluorescence spectra based on the Smoluchowski diffusion equation are also briefly discussed. Presented at the Czech-Israeli-German Symposium “Dynamical Processes in Condensed Molecular Systems”, Prague, Czech Republic, 26–30 May 1997. This work was supported in part by the Netherlands Foundation for Chemical Research (SON) with financial aid from the Netherlands Organization for Scientific Research (NWO).     

High-frequency subsurface and bulk dynamics of liquid indium

We have performed bulk and surface-sensitive inelastic x-ray scattering experiments on liquid indium with 3 meV energy resolution. The experimental data are well reproduced within a generalized hydrodynamic model including structural and microscopic relaxation processes. We find a longitudinal viscosity of 22 mPa s in the near-surface region compared to 7.4 mPa s in the bulk. The origin of the increase is associated with a slowing down of the collective dynamics in a subsurface region of 4.6 nm.     

Dynamic light scattering as a probe of orientational dynamics in confined liquid crystals

The eigenmodes of director orientational fluctuations in nematic liquid crystals in confined geometries were studied both theoretically and experimentally by dynamic light-scattering tehnique. The fundamental mode of the orientational fluctuations shows a crossover from bulk behavior, dominated by bulk elastic constant K, to surface dominated one, in which the relaxation rate is determined by the ratio of surface anchoring strength W and viscosity eta. The contribution of surface viscosity zeta is also significant when its characteristic length zeta/eta becomes comparable to the size of the confined system. It was measured in nematic liquid crystal in cylindrical pores of polycarbonate (Nuclepore) membranes to be of the order of 10 nm.     

Molecular dynamics simulations of the orientational motion of liquid chloroform at 298 K and 220K

Molecular dynamics simulations of liquid chloroform at 298 K and 220 K, using established optimized potential parameters and run on single-processor workstations, are employed to compute the first- and second-order Legendre polynomial, single-molecule orientational correlation functions describing the tumbling motion of the carbon-hydrogen bond direction. The results of the simulated Raman correlation functions compare well with their experimental counterparts from previously reported Fourier-transformed band contours of two totally symmetric vibration-rotation modes of the liquid. Simulated angular momentum, angular velocity, and intermolecular torque correlation functions are shown, and helped to characterize the insignificance of free orientational mobility within the system. Perturbation effects from rotation-vibration interaction and collision-induced intensities are present, but their effects on the correlation results are not sufficiently high to be of major significance.     

Ion solvation dynamics in supercritical fluids

We present a theoretical study of ion solvation dynamics in a supercritical solvent. Molecular dynamics simulations show a significant difference between equilibrium and nonequilibrium solvent response functions, especially pronounced at medium and low solvent densities. We propose a simple analytical theory for the nonequilibrium solvation function based on the generalized nonlinear Smoluchowski-Vlasov equation. The theory is shown to be in excellent agreement with simulation over a wide range of supercritical solvent densities.     

A model for the orientational order in liquid crystals

Summary A model for the orientational-order parameter in liquid crystals from the microscopic viewpoint and in conformity with its current understanding well established in the field of phase transitions is proposed here. This model has a close resemblance with the original ideas of Maier and Saupe. However, it is independent of the nature of molecules, rigid or flexible, and enables us to describe a phase with a single-order parameter tensor as expected. Moreover, an important advantage of this model in contrast to the prevailing ones is its, ability to separate the contributions of long-range order from local information inherent in any microscopic measurement such as by NMR and EPR techniques with some reasonable assumptions. All these are demonstrated here with the observed quadrupole splittings for different deuterium sites of long-chain molecules forming the uniaxial nematic phase. The role of molecular conformations on the observed splittings is also explicitly demonstrated by recovering quadrupole coupling constants and bond orientations at different molecular sites. These results are in reasonable agreement with available data. To speed up publication, the author of this paper has agreed to not receive the proofs for correction.     

High-temperature dynamic behavior in bulk liquid water: A molecular dynamics simulation study using the OPC and TIP4P-Ew potentials

Classical molecular dynamics simulations were performed to study the high-temperature (above 300 K) dynamic behavior of bulk water, specifically the behavior of the diffusion coefficient, hydrogen bond, and nearest-neighbor lifetimes. Two water potentials were compared: the recently proposed “globally optimal” point charge (OPC) model and the well-known TIP4P-Ew model. By considering the Arrhenius plots of the computed inverse diffusion coefficient and rotational relaxation constants, a crossover from Vogel–Fulcher–Tammann behavior to a linear trend with increasing temperature was detected at T* ≈ 309 and T* ≈ 285 K for the OPC and TIP4P-Ew models, respectively. Experimentally, the crossover point was previously observed at T* ± 315–5 K. We also verified that for the coefficient of thermal expansion α _P (T, P), the isobaric α _P (T) curves cross at about the same T* as in the experiment. The lifetimes of water hydrogen bonds and of the nearest neighbors were evaluated and were found to cross near T*, where the lifetimes are about 1 ps. For T < T*, hydrogen bonds persist longer than nearest neighbors, suggesting that the hydrogen bonding network dominates the water structure at T < T*, whereas for T > T*, water behaves more like a simple liquid. The fact that T* falls within the biologically relevant temperature range is a strong motivation for further analysis of the phenomenon and its possible consequences for biomolecular systems.     

The structure,dynamics and solvation mechanisms of ions in water from long time molecular dynamics simulations: a case study of CaCl2 (aq) aqueous solutions

Systematic long time (5–20 ns) molecular dynamics (MD) simulations have been carried out to study the structural and dynamical properties of CaCl₂ aqueous solutions over a wide range of concentrations (≤9.26 m) in this study. Our simulations reveal totally different structural characteristics of those yielded from short time (≤1 ns) MD simulations [A.A. Chialvo and J.M. Simonson, J. Chem. Phys. 119, 8052 (2003); T. Megyes, I. Bako, S. Balint, T. Grosz, and T. Radnai, J. Mol. Liq. 129, 63 (2006)]. An apparent discontinuity was found at 4–5 m of CaCl₂ in various properties including ion–water coordination number and self-diffusion coefficient of ions, which were first noticed by Phutela and Pitzer in their thermodynamic modelling [R.C. Phutela and K.S. Pitzer, J. Sol. Chem. 12, 201 (1983)]. In this study, residence time was first taken into consideration in the study of Ca²⁺–Cl^? ion pairing, and it was found that contact ion pair and solvent-sharing ion pair start to form at the CaCl₂(aq) concentrations of about 4.5 and 4 m, respectively, which may be responsible for the apparent discontinuity. In addition, the residence time of water molecules around Ca²⁺ or Cl^? showed that the hydration structures of Ca²⁺ and Cl^? are flexible with short residence time (<1 ns). It needs to be pointed out that it takes much longer simulation time for the CaCl₂–H₂O system to reach equilibrium than what was assumed in previous studies.     

Local structure and orientational ordering in liquid bromoform

The neutron diffraction data of liquid bromoform (CHBr₃) at 25°C was analysed using the Empirical Potential Structure Refinement technique in combination with H/D isotopic substitution. Compared to liquid chloroform (CHCl₃), CHBr₃ displays more spatially defined intermolecular contacts. A preference for polar stacking with collinear alignment of dipole moments is observed for the most closely approaching CHBr₃ molecules, although to a lesser extent than in chloroform. Consistent with this, and in line with dielectric spectroscopy, the Kirkwood correlation factor from the structural model of CHBr₃ is smaller than that of CHCl₃. The net antiparallel alignment of dipole moments in CHBr₃, as suggested by dielectric spectroscopy, must be due to weak but persistent long-range orientation correlations in CHBr₃, which counteract the local polar stacking.     

Ultrafast vibrational and structural dynamics of the proton in liquid water

The dynamical behavior of excess protons in liquid water is investigated using femtosecond vibrational pump-probe spectroscopy. By resonantly exciting the O-H+-stretching mode of the H9O4(+) (Eigen) hydration structure of the proton and probing the subsequent absorption change over a broad frequency range, the dynamics of the proton is observed in real time. The lifetime of the protonic stretching mode is found to be approximately 120 fs, shorter than for any other vibration in liquid water. We also observe the interconversion between the H9O4(+) (Eigen) and H5O2(+) (Zundel) hydration structures of the proton. This interconversion, which constitutes an essential step of proton transport in water, is found to occur on an extremely fast (< 100 fs) time scale.     

Non-coincidence effect and orientational dynamics in aromatic molecules

The ring breathing vibrations of aromatic molecules show an unusual non-coincidence effect, due to a poorly defined resonant coupling. This kind of non-coincidence effect has been compared within and between two couples of isotopomers, light and deuterated toluene and o-xylene, in pure substances and in dilutions with CCl₄, in a temperature range of 282–350 K. Analogous trends are shown between the physical and molecular properties, such as single particle orientational times, hydrodynamic volumes and the non-coincidence effect itself. For each couple, the vibrational and rotational dynamics, together with structural properties, can be described within a unique framework. For the first time, the dynamic trends of similar isotopomer couples have been explored, showing obvious similarities and unsuspected differences between and within each couple of the chosen molecular liquids. In particular, the hydrodynamic volume values have been calculated and interpreted within the free volume theory.     

Molecular dynamics computation of the work of ion solvation: comparison of two models of water

Clusters of the TIP4P water model with 125 and 256 molecules and with the K⁺ or K^? ions were simulated by the molecular dynamics method. The radial profiles of local density, energy, normal pressure and molecular orientation were obtained. The work of cluster formation was calculated from the normal pressure profile. The results for the TIP4P and SPC/E model of water are discussed in comparison with each other. A divergence in behaviour of water molecules in the two models was discovered.     

Molecular dynamics simulations of PVP kinetic inhibitor in liquid water and hydrate/liquid water systems

The possible effects of PVP (poly(N-vinylpyrrolidone)) on the properties of liquid and water in clathrate hydrate has been investigated using NVT molecular dynamics simulations. A model for a monomer of the PVP polymer is immersed in three systems, liquid water, a unit cell of a hydrate in liquid water with a hydrate former and a third system where some of the liquid water molecules of this last system are replaced by a PVP monomer. Both molecular dynamics simulation and integral equation theory predict hydrogen bonding between the double bonded oxygen in the PVP ring and hydrogens in water. For the composite system, the PVP monomer has a preference for hydrogen bonding to hydrogens from the water molecules at the surface of the hydrate lattice. The simulations indicate that the PVP monomer tends to orient perpendicular to the hydrate surface. For the model systems in this study PVP may form hydrogen bonds with liquid water through the double bonded oxygen in the ring. When a hydrate crystal is immersed in the liquid water phase this hydrogen bonding is shifted towards the hydrate due to a more favourable Coulomb interaction involving hydrogens from more than one water molecule at the hydrate surface. The PVP monomer has a preference for perpendicular orientation with respect to the hydrate surface. A scheme is suggested for the characterization of kinetic hydrate inhibitors based on molecular dynamics simulations and on three basic properties. In addition to the energy between the active groups of the inhibitor and hydrate water another point of focus is the free energy changes in the interactions between the inhibitor and water as the charges are changed from zero to the original model charges. In particular the difference between this integral for the (hydrate water)–(PVP monomer) interaction and the (liquid water)–(PVP inhibitor) interaction should reflect the driving forces in freezing the inhibitor out from the liquid water phase and onto the hydrate surface. The third property in the characterization scheme is the diffusivities of groups connecting to the hydrate crystal, relative to the diffusivities of the hydrate crystal. Results are presented from simulations where a small cavity with a methane model as a guest is immersed in liquid water with free methane molecules at a temperature of 150K. Changes in structure, diffusivities and energy indicate a tendency towards a more solid–like structurde around the cavity.     

Short range orientational order in nematic liquid crystals

The different approximations that have been used in applying Bethe’s cluster model to the nematic-isotropic phase transition are examined. It is shown that the introduction of a higher order term in the mean field potential of an outer molecule of the cluster improves the consistency of the theory considerably. In particular, the importance of satisfying Chang’s relation is emphasized. Calculations are presented of the long and short range order parameters, heat of transition and specific heat for different values ofz, the number of nearest neighbours around any given molecule, for both nonpolar and antiparallel near neighbour correlations. Even the new mean field potential appears to be inadequate forz=3.     

Formation and solvation dynamics of electrons in polyols

Using pump-probe transient absorption spectroscopy we studied the solvation dynamics of the electron in liquid polyalcohols: ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol and propane-1,2,3-triol. First, transmission measurements allowed us to assess that electrons were produced via two-photon ionization of the solvent with 263 nm femtosecond laser pulses, and to determine the two-photon absorption coefficient of the polyols. Second, time-resolved absorption spectra ranging from 440 to 710 nm were measured. Our study shows that the excess electron in the diols presents an intense and wide absorption band in the visible and near-IR spectral domain at early time after photoionization. Then, for the first tens of picoseconds the electron spectrum shifts toward the blue domain and its bandwidth decreases as the red part of the initial spectrum drops rapidly while the blue part hardly evolves. Using Bayesian data analysis method, the observed picosecond solvation dynamics were reconstructed with three models: a two-step mechanism and two continuous relaxation models. Comparison between the ability of models to reproduce the experimental kinetics is in favor of a heterogeneous continuous relaxation. Recent results obtained in propane-1,2,3-triol show that the electron solvation dynamics is very fast in this solvent despite its high viscosity and highlight the role of the OH group in that process.