Effect of chemical structure on the isobaric and isochoric fragility in polychlorinated biphenyls

Pressure-volume-temperature data, along with dielectric relaxation measurements, are reported for a series of polychlorinated biphenyls (PCB), differing in the number of chlorine atoms on their phenyl rings. Analysis of the results reveals that with increasing chlorine content, the relaxation times of the PCB become governed to a greater degree by density rho relative to the effect of temperature T. This result is consistent with the respective magnitudes of the scaling exponent gamma yielding superpositioning of the relaxation times measured at various temperatures and pressures, when plotted versus rho(gamma)/T. While at constant (atmospheric) pressure, fragilities for the various PCB are equivalent, the fragility at constant volume varies inversely with chlorine content. Evidently, the presence of bulkier chlorine atoms on the phenyl rings magnifies the effect which the density has on the relaxation dynamics.     

Molecular dynamics investigation of a density-driven glass transition in a liquid crystal system

Molecular dynamics simulations are carried out to address the density-driven glass transition in a system of rodlike particles that interact with the Gay-Berne potential. Since crystallization occurs in this system on the time scale of the simulations, direct simulation of the glass transition is not possible. Instead, glasses with isotropic orientational order are heated to a temperature T, and the relaxation times by which nematic orientational order develops are determined. These relaxation times appear to diverge at a critical density rho(c); i.e., the system can equilibrate at rhorho(c) (at the temperature T). The relaxation times follow a power-law scaling as the critical density is approached, suggesting that this density-driven glass transition concurs with mode coupling theory.     

The effects of solute-solvent electrostatic interactions on solvation dynamics in supercritical CO2

We present here the results of molecular-dynamics simulation of solvation dynamics in supercritical CO(2) at a temperature of about 1.05T(c), where T(c) is the critical temperature, and at a series of densities ranging from 0.4 to 2.0 of the critical density rho(c). We focus on electrostatic solvation dynamics, representing the electronic excitation of the chromophore as a change in its charge distribution from a quadrupolar-symmetry ground state to a dipolar excited state. Two perturbations are considered, corresponding to different magnitudes of solute excited-state dipoles, denoted as d5 and d8. The d8 solute is more attractive, leading to a larger enhancement in CO(2) clustering upon solute electronic excitation. This has a large impact on solvation dynamics, especially at densities below rho(c). At these densities, solvation dynamics is much slower for the d8 than for the d5 solute. For both solutes, solvation dynamics becomes faster at densities above rho(c) at which solvent clustering diminishes. We show that the slowest solvation time scale is associated with solvent clustering and we relate it to solute-solvent mutual translational diffusion and the extent of change in effective local density resulting from solute electronic excitation.     

Application of Schrödinger equation to study the tunnelling dynamics of proton transfer in the hydrogen bond of 2,5-dinitrobenzoic acid: proton T1 T1rho, and deuteron T1 relaxation methods

Temperature measurements of proton T1 (24.7 MHz), deuteron (deuterated hydroxyl group) T1 (55.2 MHz), and proton T1(rho) (B1 = 9 G) spin-lattice relaxation times of 2,5-dinitrobenzoic acid have been performed. An analysis of present experimental data together with previously published proton T1 (55.2 MHz) data has revealed the following molecular motions: proton/deuteron transfer in the hydrogen bond and two-site hopping of the whole dimer. It is shown that the proton-transfer dynamics are characterized by two correlation times tau(ov) and tau(tu), describing two fundamentally different motional processes, namely, thermally activated jumps over the barrier and tunneling through the barrier. The temperature dependence of 1/tau(tu) is the solution of Schr?dinger's equation, which also yields the temperature T(tun), where begins the tunnel pathway for proton transfer. A new equation for the spectral density function of complex motion consisting of the three motions is derived. The third motion (two-site hopping of the whole dimer characterized by tau(lib) correlation time) is responsible for a proton T1(rho) minimum in high temperatures, just below the melting point. Such a minimum is not reached by T1 temperature dependencies. The minimum of T1(rho) assigned to the classical hopping of a hydrogen-bonded proton occurs in the same low-temperature regime in which the flattening of the temperature dependencies of T1 points to the dominance of incoherent tunneling. This experimental fact denies the known theories predicting the intermediate temperature regime where a smooth transition between classical and quantum tunneling dynamics is expected. The fit of the derived theoretical equations to the experimental data T1(rho) and T1 is satisfactory. The correlation times obtained for deuterons indicate deuteron-transfer dynamics much slower than proton-transfer dynamics. It is concluded that the classical proton transfer takes place over the whole temperature regime, while the incoherent tunneling occurs below 46.5 (hydrogen) or 87.2 K (deuterium) only.     

Relating linear vibrational spectroscopy to condensed-phase hydrogen-bonded structures: Liquid-to-supercritical water

The pressure and temperature-dependent linear absorption spectrum of partially deuterated water HOD dissolved in heavy water D(2)O was measured in the OH-stretching spectral region. The temperature was varied in the interval of 298 K相似文献   

Equilibrium conformational dynamics of a polymer in a solvent

Molecular dynamics simulations were used to study the conformational dynamics of a bead-spring model polymer in an explicit solvent under good solvent conditions. The dynamics of the polymer chain were investigated using an analysis of the time autocorrelation functions of the Rouse coordinates of the polymer chain. We have investigated the variation of the correlation functions with polymer chain length N, solvent density rho, and system size. The measured initial decay rates gamma(p) of the correlation functions were compared with the predictions from a theory of polymer dynamics which uses the Oseen tensor to describe hydrodynamic interactions between monomers. Over the range of chain lengths considered (N = 30-60 monomers), the predicted scaling of gamma(p) proportional to N(-3nu) was observed at high rho, where nu is the polymer scaling exponent. The predicted gamma(p) are generally higher than the measured values. This discrepancy increases with decreasing rho, as a result in the breakdown in the conditions required for the Oseen approximation. The agreement between theory and simulation at high rho improves considerably if the theoretical expression for gamma(p) is modified to avoid sum-to-integral approximations, and if the values of (R(p)2), which are used in the theory, are taken directly from the simulation rather than being calculated using approximate scaling relations. The observed finite-size scaling of gamma(p) is not quantitatively consistent with the theoretical predictions.     

Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids

The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev. Lett. 103, 170601 (2009); J. Chem. Phys. 134, 214503 (2011)]. We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations of the Kob-Andersen binary Lennard-Jones mixture. By varying the range of the forces via a shifted-forces cutoff, results for the thermodynamics, dynamics, and structure show that the determining factor for getting the correct statics and dynamics is not whether or not the attractive forces per se are included in the simulations. What matters is whether or not interactions are included from all particles within the first coordination shell - the attractive forces can thus be ignored, but only at extremely high densities. The recognition of the importance of a local shell in condensed fluids goes back to van der Waals; our results confirm this idea and thereby the basic picture of the old hole and cell theories for simple condensed fluids.     

Low-frequency cooperative dynamics in L-, D-, and DL-alanine crystals: a 13C and 15N cross-polarization magic-angle-spinning NMR study

Knowledge of the dynamical changes in molecular configurations in various amino acid structures over a wide range of time scales is important since such changes may influence the structural transformations and the diverse biological functionalities of proteins. Using the temperature dependence of the rotating-frame NMR spin-lattice relaxation times T(1rho) of protons as a probe, we have investigated the low-frequency (approximately 60-100 kHz) dynamics in the crystal structures of L-, D-, and DL- alanine (C(12)H(28)O(8)N(4)) polymorphs. The proton relaxation times T(1rho) were obtained from (13)C <-- (1)H and (15)N <-- (1)H cross-polarization magic-angle-spinning NMR experiments over a temperature range of 192-342 K. The data reveal that the time scales of these low-frequency dynamical processes are distinctly different from the localized, high-frequency rotational motion of methyl and amine groups. The strongly asymmetric T(1rho) versus temperature curves and the subtle dynamical differences between the DL-alanine and the L- and d-enantiomorphs indicate that these low-frequency processes are cooperative in nature and are sensitive to molecular packing.     

Structure of star-burst dendrimers: a comparison between small angle x-ray scattering and computer simulation results

We investigated the generation dependent shape and internal structure of star-burst dendrimers under good solvent conditions using small angle x-ray scattering and molecular modeling. Measurements have been performed on poly(amidoamine) dendrimers with generations ranging from g=0 up to g=8 at low concentrations in methanol. We described the static form factor P(q) by a model taking into account the compact, globular shape as well as the loose, polymeric character of dendrimers. Monomer distributions within dendrimers are of special interest for potential applications and have been characterized by the pair correlation function gamma(r), as well as by the monomer and end-group density profile, rho(r) and rho(e)(r), respectively. Monomer density profiles and gamma(r) can be derived from P(q) by modeling and via a model independent approach using the inverse Fourier transformation algorithm first introduced by Glatter. Experimental results are compared with computer simulations performed for single dendrimers of various generations using the cooperative motion algorithm. The simulation gives direct access to gamma(r) and rho(r), allows an independent determination of P(q), and yields in addition to the scattering experiment information about the distribution of the end groups. Excellent qualitative agreement between experiment and simulation has been found.     

Structural anomalies for a three dimensional isotropic core-softened potential

Using molecular dynamics simulations we investigate the structure of a system of particles interacting through a continuous core-softened interparticle potential. We found for the translational order parameter t a local maximum at a density rho(t-max) and a local minimum at rho(t-min)>rho(t-max). Between rho(t-max) and rho(t-min), the t parameter anomalously decreases upon increasing pressure. For the orientational order parameter Q(6) a maximum was observed at a density rho(t-max)相似文献   

Local density inhomogeneities and dynamics in supercritical water: A molecular dynamics simulation approach

Molecular dynamics atomistic simulations in the canonical ensemble (NVT-MD) have been used to investigate the "Local Density Inhomogeneities and their Dynamics" in pure supercritical water. The simulations were carried out along a near-critical isotherm (Tr = T/Tc = 1.03) and for a wide range of densities below and above the critical one (0.2 rho(c) - 2.0 rho(c)). The results obtained reveal the existence of significant local density augmentation effects, which are found to be sufficiently larger in comparison to those reported for nonassociated fluids. The time evolution of the local density distribution around each molecule was studied in terms of the appropriate time correlation functions C(Delta)rhol(t). It is found that the shape of these functions changes significantly by increasing the density of the fluid. Finally, the local density reorganization times for the first and second coordination shell derived from these correlations exhibit a decreasing behavior by increasing the density of the system, signifying the density effect upon the dynamics of the local environment around each molecule.     

Explicit hydrogen molecular dynamics simulations of hexane deposited onto graphite at various coverages

We present results of molecular dynamics (MD) computer simulations of hexane (C6H14) adlayers physisorbed onto a graphite substrate for coverages in the range 0.5 < or = rho < or = 1 monolayers. The hexane molecules are simulated with explicit hydrogens, and the graphite substrate is modeled as an all-atom structure having six graphene layers. At coverages above about rho congruent with 0.9 the low-temperature herringbone solid loses its orientational order at T(1) = 140 +/- 3 K. At rho = 0.878, the system presents vacancy patches and T(1) decreases to ca. 100 K. As coverage decreases further, the vacancy patches become larger and by rho = 0.614 the solid is a connected network of randomly oriented islands and there is no global herringbone order-disorder transition. In all cases we observe a weak nematic mespohase. The melting temperature for our explicit-hydrogen model is T(2) = 160 +/- 3 K and falls to ca. 145 K by rho = 0.614 (somewhat lower than seen in experiment). The dynamics seen in the fully atomistic model agree well with experiment, as the molecules remain overall flat on the substrate in the solid phase and do not show anomalous tilting behavior at any phase transition observed in earlier simulations in the unified atom (UA) approximation. Energetics and structural parameters also are more reasonable and, collectively, the results from the simulations in this work demonstrate that the explicit-hydrogen model of hexane is substantially more realistic than the UA approximation.     

Thermodynamic scaling of diffusion in supercooled Lennard-Jones liquids

The manner in which the intermolecular potential u(r) governs structural relaxation in liquids is a long standing problem in condensed matter physics. Herein, we show, in agreement with recent experimental results, that diffusion coefficients for simulated Lennard-Jones m-6 liquids (8 < or = m < or = 36) in normal and moderately supercooled states are a unique function of the variable rhogamma/T, where rho is density and T is temperature. The scaling exponent gamma is a material specific constant whose magnitude is related to the steepness of the repulsive part of u(r), evaluated around the distance of closest approach between particles probed in the supercooled regime. Approximations of u(r) in terms of inverse power laws are also discussed.     

Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments. As an example, in the framework of SLLFT, the spinodal curve for the iPP/PEOC blend is predicted at the low molecular weights that are used in the simulations.     

Density scaling and relaxation of the Pauli principle

The relaxation of the Pauli principle associated with density scaling is examined. Scaling the density has been investigated in the development of density functional computational methods with higher accuracy. Scaling the density by rho(r)(zeta)=rho(r)zeta reduces the number of electrons to M=Nzeta when zeta>1. The minimum kinetic energy of the scaled density, T(s)[rhozeta], can be scaled back to the N-electron system by multiplying the M-electron Kohn-Sham-type occupation numbers by zeta to produce T(zeta)[rho]. This relaxes the Pauli principle when the orbital occupation numbers are greater than 1 in the N-electron system. The effects of antisymmetry on solutions to the Kohn-Sham equations are examined for Ne and the Be isoelectronic series. The changes in T(zeta)[rho] and the exchange energy E(xzeta)[rho] when zeta is varied show that these two quantities are inextricably linked.     

Self-diffusion of supercritical water in extremely low-density region

The self-diffusion coefficient D for super- and subcritical water is determined by using the proton pulsed-field-gradient spin echo method at high temperatures and low densities. The density of water is ranged in the steamlike region from 0.0041 to 0.0564 g [corrected] cm(-3) at a supercritical temperature of 400 degrees C, also at 0.0041-0.0079 and 0.0041-0.0462 g [corrected] cm(-3) (the steam-branch densities on the coexistence curve and lower) at 200 and 300 degrees C, respectively. The density is precisely determined on the basis of the PVT dependence of the proton chemical shift. The density-diffusivity products in the zero-density limit divided by the square root of the temperature, (rho D)0/square root of T, are 0.94, 1.17, and 1.35 mg m(-1) s(-1) K(-1/2) (mg=10(-3)g) [corrected] at 200, 300, and 400 degrees C, respectively. The (rhoD)0/square root of T obtained decreases with decreasing temperature and is significantly smaller than the temperature-independent value from the hard sphere model, 1.95 mg [corrected] m(-1) s(-1) K(-1/2). The marked temperature dependence reflects the presence of the strong attractive interaction between a pair of water molecules. The magnitude of the experimental D values and the temperature dependence are well reproduced by the molecular dynamics simulation using TIP4P-FQ model. The initial slope of the product rhoD/square root of T against rho is slightly negative at 300 and 400 [corrected] degrees C.     

The role of pressure in rubber elasticity

We describe a series of molecular dynamics computations that reveal an intimate connection at the atomic scale between difference stress (which resists stretches) and pressure (which resists volume changes) in an idealized elastomer, in contrast to the classical theory of rubber elasticity. Our simulations idealize the elastomer as a "pearl necklace," in which the covalent bonds are stiff linear springs, while nonbonded atoms interact through a Lennard-Jones potential with energy epsilon(LJ) and radius sigma(LJ). We calculate the difference stress t(11)-(t(22)+t(33))/2 and mean stress (t(11)+t(22)+t(33))/3 induced by a constant volume extension in the x(1) direction, as a function of temperature T and reduced density rho(*)=Nsigma(IJ) (3)/nu. Here, N is the number of atoms in the simulation cell and nu is the cell volume. Results show that for rho(*)<1, the difference stress is purely entropic and is in good agreement with the classical affine network model of rubber elasticity, which neglects nonbonded interactions. However, data presented by van Krevelen [Properties of Polymers, 3rd ed. (Elsevier, Amsterdam, 1990), p. 79] indicate that rubber at standard conditions corresponds to rho(*)=1.2. For rho(*)>1, the system is entropic for kT/epsilon(LJ)>2, but at lower temperatures the difference stress contains an additional energy component, which increases as rho(*) increases and temperature decreases. Finally, the model exhibits a glass transition for rho(*)=1.2 and kT/epsilon(LJ) approximately 2. The atomic-scale processes responsible for generating stress are explored in detail. Simulations demonstrate that the repulsive portion of the Lennard-Jones potential provides a contribution sigma(nbr)>0 to the difference stress, the attractive portion provides sigma(nba) approximately 0, while the covalent bonds provide sigma(b)<0. In contrast, their respective contributions to the mean stress satisfy Pi(nbr)<0, Pi(nba)>0, and Pi(b)<0. Analytical calculations, together with simulations, demonstrate that mean and difference stresses are related by sigma(nbr)=-APi(nbr)P(2)(theta(b)), sigma(b)=BPi(b)P(2)(theta(b)), where P(2)(theta(b)) is a measure of the anisotropy of the orientation of the covalent bonds, and A and B are coefficients that depend weakly on rho(*) and temperature. For high values of rho(*), we find that [sigma(nbr)]>[sigma(b)], and in this regime our model predicts behavior that is in good agreement with experimental data of D.L. Quested et al. [J. Appl. Phys. 52, 5977 (1981)] for the influence of pressure on the difference stress induced by stretching solithane.     

High density amorphous ices: disordered water towards close packing

The structure of amorphous ice under pressure has been studied by molecular dynamics at 160 K. The starting low-density phase undergoes significant changes as the density increases, and at rho=1.51 g/cm(3) our calculated g(OO)(r) is in excellent agreement with in situ neutron diffraction data obtained at 1.8 GPa and 100 K on very high density amorphous ice made at 150 K. As the system is further compressed, in the theoretical simulations, up to rho=1.90 g/cm(3), the structural modifications are continuous up to the highest density. The analysis of orientational distributions reveals that dense amorphous ice is characterized by major distortions of the tetrahedral geometry, and that the pressure structural changes, already observed experimentally at lower densities, can be interpreted as a trend towards a disordered closed-packed structure.