Molecular dynamics studies of melting and some liquid-state properties of 1-ethyl-3-methylimidazolium hexafluorophosphate [emim][PF6

Molecular dynamics simulations are used to study the liquid-state properties and melting of 1-ethyl-3-methylimidazolium hexafluorosphosphate [emim][PF6] using the force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] and geometric constants from crystallographic data. The structures of the solid and liquid states are characterized by carbon-carbon, carbon-phosphorous, and phosphorous-phosphorous radial distribution functions. Spatial correlations among the ions are strong in the liquid state. The cohesive energy density and the temperature dependences of the molar volume and density of the liquid have been computed. The melting point is determined by equilibrating the solid-state supercells in which void defects have been introduced to eliminate the free-energy barrier for the formation of a solid-liquid interface. The computed melting point is 375+/-10 K, which is approximately 10% higher than the experimental value of 333 K.     

Terahertz spectroscopy and solid-state density functional theory simulations of the improvised explosive oxidizers potassium nitrate and ammonium nitrate

Terahertz spectroscopy provides a noninvasive and nondestructive method for detecting and identifying concealed explosives. In this work, the room-temperature and cryogenic terahertz spectra of two common improvised explosive oxidizers, namely, potassium nitrate (KN) and ammonium nitrate (AN), are presented, along with detailed solid-state density functional theory (DFT) analyses of the crystalline structures and spectral features. At both 294 and 78 K, KN exhibits two terahertz absorption features below 100 cm(-1) that have been assigned through DFT simulations to arise from hindered nitrate rotations in the KN-II crystalline polymorph. The terahertz spectrum of AN exhibits a pronounced temperature dependence. The 294 K spectrum is free of any absorptions, whereas the 78 K spectrum consists of several narrow and intense peaks. The origin of this large difference is the polymorphic transition that occurs during cooling of AN, where room-temperature AN-IV is converted to AN-V at 255 K. The 78 K terahertz spectrum of AN is assigned here to various ion rotations and translations in the AN-V polymorph lattice. The analysis of the room-temperature AN-IV terahertz spectrum proved to be more complicated. The solid-state DFT simulations predicted that the room-temperature crystal structure of AN is not very well described using the standard Pmmn space-group symmetry as previously believed. The AN-IV polymorph actually belongs to the Pmn2(1) space group, and the perceived Pmmn symmetry results from vibrational averaging through nitrate rotations. This newly observed Pmn2(1) crystal symmetry for room-temperature AN is the reason for the absence of absorption features in the 294 K terahertz spectrum of AN and provides new insight into the polymorphic transitions of this ionic solid.     

Simulations of the solid, liquid, and melting of 1-n-butyl-4-amino-1,2,4-triazolium bromide

Molecular dynamics simulations are used to study the solid and liquid properties and to predict the melting point of 1-n-propyl-4-amino-1,2,4-triazolium bromide ([patr][Br]) using a force field based on the one developed by Canongia Lopes et al. (J. Phys. Chem. B 2004, 108, 2038) for dialkyl substituted imidazolium salts, which was modified by including terms from the general AMBER force field. Electrostatic charges for the intermolecular interactions were determined from gas-phase ab initio electron structure calculations of the triazolium cation. Simulations of the solid state at 100 K reproduced the experimental density to within 4%. Simulations from 100 K to the melting point and the liquid from 333 to 500 K were performed to determine the temperature dependence of the densities of the two phases. The structures of the solid and liquid phases are characterized with radial distribution functions, which show that there are strong spatial correlations among neighboring ion pairs in liquid [patr][Br]. The dynamic behavior of the ions in the liquid state is also studied by computing velocity autocorrelation functions and the mean-square displacements between the ions. The melting point is determined by simulating void-induced melting. Changes in the density, intermolecular energy, and Lindemann index are used as indicators of the melting transition. The computed melting point is 360 +/- 10 K, which is within 10% of the experimental value 333 K.     

磷酸二氢铵水溶液构型能删和径向分布函数的分子动力学模拟

采用分子动力学模拟对不同温度下磷酸二氢铵水溶液的构型能和径向分布函数进行了研究．磷酸二氢根被看作七节点模型,铵离子被看作五节点模型,而水分子则被看作简单点电荷模型．在饱和温度附近,体系局域粒子数密度有波动．373-400K的溶液势能增长缓慢表明磷酸二氧铵部分分解．磷酸二氢根中的氧原子与铵离子中氢原子的径向分布函数在三种不同温度下呈现明显不同,表明溶液中平均氢键数目随温度的变化明显改变．温度对磷酸二氢根中的氧原子和氧原子的结合有一定的影响,而在饱和溶液中有更多的生长基无产生．     

Experimental determination of the NH4NO3/(NH4)2SO4/H2O phase diagram

We have studied the thermodynamic properties of the ammonium nitrate/ammonium sulfate/water system using differential scanning calorimetry and infrared spectroscopy of thin films at low temperatures. This is the first study focused on low temperatures, as previous experimental work on this system has been at 273 K and above. We have combined our experimental results with melting point data from the literature at high temperatures to create a solid/liquid phase diagram of the ammonium nitrate/ammonium sulfate/water system for temperatures below 343 K. Using phase diagram theory and Alkemade lines, we predict which solids are stable at equilibrium for all concentrations within the studied region. We also observed the decomposition of a solid at low temperatures which has not previously been reported. Finally, we have compared our predicted solids and final melting temperatures to the Aerosol Inorganics Model (AIM).     

Refined potential model for atomistic simulations of ionic liquid [bmim][PF6

Refined parameters of an atomistic interaction potential model for the room temperature ionic liquid 1-n-butyl,3-methylimidazolium hexafluorophosphate are presented. Classical molecular dynamics simulations have been carried out to validate this fully flexible all-atom model. It predicts the density of the liquid at different temperatures between 300 and 500 K within 1.4% of the experimental value. Intermolecular radial distribution functions and the spatial distribution functions obtained from the new model are in close agreement with ab initio simulations. The calculated diffusion coefficients of ions and the surface tension of the liquid agree well with experiment.     

Isotope quantum effects in water around the freezing point

We have measured the difference in electronic structure factors between liquid H(2)O and D(2)O at temperatures of 268 and 273 K with high energy x-ray diffraction. These are compared to our previously published data measured from 279 to 318 K. We find that the total structural isotope effect increases by a factor of 3.5 over the entire range, as the temperature is decreased. Structural isochoric temperature differential and isothermal density differential functions have been used to compare these data to a thermodynamic model based upon a simple offset in the state function. The model works well in describing the magnitude of the structural differences above approximately 310 K, but fails at lower temperatures. The experimental results are discussed in light of several quantum molecular dynamics simulations and are in good qualitative agreement with recent temperature dependent, rotationally quantized rigid molecule simulations.     

A classical polarizable model for simulations of water and ice

We develop a classical rigid polarizable model of water for molecular simulations of water and ice. The model uses the Rowlinson five-site geometry: oxygen bearing the Lennard-Jones interaction and linearly polarizable point dipole, two positively charged hydrogens, and two massless negative charges placed symmetrically off oxygen so that the experimental dipole moment is reproduced. The target properties are the densities of water and ice Ih, diffusivity, enthalpies of fusion and vaporization, and the ice Ih melting point. The surface tension at lower temperatures is by 7% underestimated whereas the dielectric constant by 6% overestimated. Diffusivity and viscosity worsen at higher temperatures, although the Stokes radius is overestimated only by 2-7%. The ice Ih melting temperature is 260 K and the temperature of maximum density is 269 K. Rescaling the charges by a factor of 1.01 and Lennard-Jones energy by 1.0201 improves the melting point and energy-related quantities but shifts the agreement of kinetic properties to higher temperatures. For the model we propose abbreviation POL4D.     

Molecular dynamics simulation of the energetic room-temperature ionic liquid, 1-hydroxyethyl-4-amino-1,2,4-triazolium nitrate (HEATN)

Molecular dynamics (MD) simulations have been performed to investigate the structure and dynamics of an energetic ionic liquid, 1-hydroxyethyl-4-amino-1,2,4-triazolium nitrate (HEATN). The generalized amber force field (GAFF) was used, and an electronically polarizable model was further developed in the spirit of our previous work (Yan, T.; Burnham, C. J.; Del Popolo, M. G.; Voth, G. A. J. Phys. Chem. B 2004, 108, 11877). In the process of simulated annealing from a liquid state at 475 K down to a glassy state at 175 K, the MD simulations identify a glass-transition temperature region at around 250-275 K, in agreement with experiment. The self-intermediate scattering functions show vanishing boson peaks in the supercooled region, indicating that HEATN may be a fragile glass former. The coupling/decoupling of translational and reorientational ion motion is also discussed, and various other physical properties of the liquid state are intensively studied at 400 K. A complex hydrogen bond network was revealed with the calculation of partial radial distribution functions. When compared to the similarly sized 1-ethyl-4-methyl-1,4-imidazolium nitrate ionic liquid, EMIM+/NO3-, a hydrogen bond network directly resulting in the poorer packing efficiency of ions is observed, which is responsible for the lower melting/glass-transition point. The structural properties of the liquid/vacuum interface shows that there is vanishing layering at the interface, in accordance with the poor ion packing. The effects of electronic polarization on the self-diffusion, viscosity, and surface tension of HEATN are found to be significant, in agreement with an earlier study on EMIM+/NO3- (Yan, T.; Burnham, C. J.; Del Popolo, M. G.; Voth, G. A. J. Phys. Chem. B 2004, 108, 11877).     

Molecular dynamics simulations of melting and the glass transition of nitromethane

Molecular dynamics simulations have been used to investigate the thermodynamic melting point of the crystalline nitromethane, the melting mechanism of superheated crystalline nitromethane, and the physical properties of crystalline and glassy nitromethane. The maximum superheating and glass transition temperatures of nitromethane are calculated to be 316 and 160 K, respectively, for heating and cooling rates of 8.9 x 10(9) Ks. Using the hysteresis method [Luo et al., J. Chem. Phys. 120, 11640 (2004)] and by taking the glass transition temperature as the supercooling temperature, we calculate a value of 251.1 K for the thermodynamic melting point, which is in excellent agreement with the two-phase result [Agrawal et al., J. Chem. Phys. 119, 9617 (2003)] of 255.5 K and measured value of 244.73 K. In the melting process, the nitromethane molecules begin to rotate about their lattice positions in the crystal, followed by translational freedom of the molecules. A nucleation mechanism for the melting is illustrated by the distribution of the local translational order parameter. The critical values of the Lindemann index for the C and N atoms immediately prior to melting (the Lindemann criterion) are found to be around 0.155 at 1 atm. The intramolecular motions and molecular structure of nitromethane undergo no abrupt changes upon melting, indicating that the intramolecular degrees of freedom have little effect on the melting. The thermal expansion coefficient and bulk modulus are predicted to be about two or three times larger in crystalline nitromethane than in glassy nitromethane. The vibrational density of states is almost identical in both phases.     

Surface tension and its temperature coefficient of molten tin determined with the sessile drop method at different oxygen partial pressures

The surface tension of molten tin has been determined by the sessile drop method at temperatures ranging from 523 to 1033 K and in the oxygen partial pressure (P(O(2))) range from 2.85 x 10(-19) to 8.56 x 10(-6) MPa, and its dependence on temperature and oxygen partial pressure has been analyzed. At P(O(2))=2.85 x 10(-19) and 1.06 x 10(-15) MPa, the surface tension decreases linearly with the increase of temperature and its temperature coefficients are -0.151 and -0.094 mN m(-1) K(-1), respectively. However, at high P(O(2)) (3.17 x 10(-10), 8.56 x 10(-6) MPa), the surface tension increases with the temperature near the melting point (505 K) and decreases above 723 K. The surface tension decrease with increasing P(O(2)) is much larger near the melting point than at temperatures above 823 K. The contact angle between the molten tin and the alumina substrate is 158-173 degrees, and the wettability is poor.     

Uptake of silver from AgNO3 salt by Zeolite-13X

Isotherms of silver uptake by zeolite-13X from AgNO₃ at temperatures /323-563 K/ around the melting point of the nitrate are reported. Measurements of silver uptake have been carried out by a neutron activation method. At temperatures below the melting point the Ag⁺ uptake is exchange dominant while above the melting point the exchange accompanies substantial AgNO₃ inclusion. The overall process of Ag⁺ uptake from both the powder and the melt is endothermic within the temperature range employed.     

The phase diagram of ammonium nitrate

The pressure-temperature (P-T) phase diagram of ammonium nitrate (AN) [NH(4)NO(3)] has been determined using synchrotron x-ray diffraction (XRD) and Raman spectroscopy measurements. Phase boundaries were established by characterizing phase transitions to the high temperature polymorphs during multiple P-T measurements using both XRD and Raman spectroscopy measurements. At room temperature, the ambient pressure orthorhombic (Pmmn) AN-IV phase was stable up to 45 GPa and no phase transitions were observed. AN-IV phase was also observed to be stable in a large P-T phase space. The phase boundaries are steep with a small phase stability regime for high temperature phases. A P-V-T equation of state based on a high temperature Birch-Murnaghan formalism was obtained by simultaneously fitting the P-V isotherms at 298, 325, 446, and 467 K, thermal expansion data at 1 bar, and volumes from P-T ramping experiments. Anomalous thermal expansion behavior of AN was observed at high pressure with a modest negative thermal expansion in the 3-11 GPa range for temperatures up to 467 K. The role of vibrational anharmonicity in this anomalous thermal expansion behavior has been established using high P-T Raman spectroscopy.     

Relation between the melting temperature and the temperature of maximum density for the most common models of water

Water exhibits a maximum in density at normal pressure at 4 degrees above its melting point. The reproduction of this maximum is a stringent test for potential models used commonly in simulations of water. The relation between the melting temperature and the temperature of maximum density for these potential models is unknown mainly due to our ignorance about the melting temperature of these models. Recently we have determined the melting temperature of ice I(h) for several commonly used models of water (SPC, SPC/E, TIP3P, TIP4P, TIP4P/Ew, and TIP5P). In this work we locate the temperature of maximum density for these models. In this way the relative location of the temperature of maximum density with respect to the melting temperature is established. For SPC, SPC/E, TIP3P, TIP4P, and TIP4P/Ew the maximum in density occurs at about 21-37 K above the melting temperature. In all these models the negative charge is located either on the oxygen itself or on a point along the H-O-H bisector. For the TIP5P and TIP5P-E models the maximum in density occurs at about 11 K above the melting temperature. The location of the negative charge appears as a geometrical crucial factor to the relative position of the temperature of maximum density with respect to the melting temperature.     

A molecular dynamics simulation of the melting points and glass transition temperatures of myo- and neo-inositol

The heat of sublimation, density, melting point, and glass transition temperature are calculated for myo- and neo-inositol, using the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field and molecular dynamics techniques. Our results show that the calculated heats of sublimation and density are very close to the experimental values for both compounds. Furthermore, our simulated melting temperatures for myo- and neo-inositol also compare very well to the experimentally obtained data. The glass transition temperatures for myo- and neo-inositol have been calculated to be ca. 494 K and ca. 518 K, respectively, and the shape of the volume versus temperature plots produced are typical for a glass transition. As a result, it is our view that the COMPASS force field suitably describes these two compounds in molecular simulations and that molecular dynamics techniques, combined with this force field, can be used to simulate the melt and glass transitions for such molecules.     

Molecular dynamics simulation of titanium dioxide nanoparticle sintering

Nanoparticles have been an area of active research in recent years due to their properties, which can be greatly different from the bulk. In this work, we study the sintering of TiO2 nanoparticles using molecular dynamics simulations. Such sintering occurs in flame reactors where nanotitania is prepared via the chloride process. Decrease in free energy due to reduction in surface area is the main driving force for sintering of particles. Simulations, at various starting temperatures and orientations, indicate that the process of sintering is strongly affected by temperature and initial orientation. Extremely high diffusion of ions in the neck region of sintering nanoparticles supports the idea that solid-state diffusion is significant in metal-oxide nanoparticle sintering. It is found that the dipole-dipole interaction between sintering nanoparticles plays a very important role at temperatures away from the melting point. The duration of the simulation is not enough to observe the complete sintering process, but important initial stages are well studied.     

Uptake of small oxygenated organic molecules onto ammonium nitrate under upper tropospheric conditions

The uptake of formic (C1), propanoic (C3), butanoic (C4), and pentanoic (C5) acids onto ammonium nitrate (AN) has been investigated as a function of temperature and relative humidity using a Knudsen cell flow reactor coupled with FTIR-reflection absorption spectroscopy (FTIR-RAS). The uptake of acetone and methanol onto AN was also briefly studied. Initial uptake coefficients (gamma) were determined over the temperature range 200-240 K. Formic, propanoic, and butanoic acids exhibited efficient but temperature-dependent uptake on AN, with larger uptake coefficients observed at lower temperatures. Pentanoic acid was not taken up by AN under any of the conditions studied. Uptake of acetone and methanol onto AN was observed, but in insignificant amounts under atmospherically relevant conditions. Infrared spectra revealed that propanoic and butanoic acids ionized on the surface, despite the fact that the AN films were effloresced. Formic acid reacted with the AN film to produce ammonium formate and ionized nitric acid. Adding small amounts of water vapor (4% RH) to the chamber resulted in dramatically increased gamma values for all of the acids. Furthermore, the IR spectra showed the formation of a liquid layer when propanoic and butanoic acids adsorbed on the surface at RH = 20% and greater. Liquid water features were not observed at a similar relative humidity in the absence of the acids. These results show that small organic acids can be efficiently scavenged by AN and lead to enhanced water uptake under upper tropospheric conditions.     

Thermal decomposition of the high-performance oxidizer ammonium dinitramide under pressure

Ammonium dinitramide (ADN) is a promising new oxidizer for solid propellants because it possesses both high oxygen balance and high energy content, and does not contain halogen atoms. A necessary characteristic of solid propellants is chemical stability under various conditions. This study focused on the thermal decomposition mechanism of ADN under pressurized conditions. The pressure was adjusted from 0.1 to 6 MPa, while ADN was heated at a constant rate. The exothermal behavior and the decomposition products in the condensed phase during heating were measured simultaneously using pressure differential scanning calorimetry (PDSC) and Raman spectrometry. PDSC analyses showed the multiple stages of exotherms after melting. The exothermal behavior at low temperatures varied with pressure. Analysis of the decomposition products indicated that ammonium nitrate (AN) was generated during decomposition of ADN at all pressures. At normal pressure, AN was produced at the same time as start of exotherm. However, the temperature at which the ratio of ADN in chemical species in the condensed phase began to decrease under high pressure was higher than that at atmospheric pressure despite the existence of significant exotherm. At initial stage, thermal decomposition of ADN that does not generate AN was thought to be promoted by increased pressure.     

An experimental study of melting of CCl4 in carbon nanotubes

We report dielectric relaxation spectroscopy measurements of the melting point of carbon tetrachloride confined within open-tip multi-walled carbon nanotubes with two different pore diameters, 4.0 and 2.8 nm. In both cases, a single transition temperature well above the bulk melting point was obtained for confined CCl4. These results contrast with what was obtained in our previous measurements using carbon nanotubes with a pore diameter of 5.0 nm, where multiple transition temperatures both above and below the bulk melting point of CCl4 were observed. Our experimental measurements are consistent with our recent molecular simulation results (F. R. Hung, B. Coasne, E. E. Santiso, K. E. Gubbins, F. R. Siperstein and M. Sliwinska-Bartkowiak, J. Chem. Phys., 2005, 122, 144706). Although the simulations overestimate the temperatures in which melting upon confinement occurs, both simulations and experiments suggest that all regions of adsorbate freeze at the same temperature, and that freezing occurs at higher temperatures upon reduction of the pore diameter.     

Negative thermal expansion of water in hydrophobic nanospaces

The density and intermolecular structure of water in carbon micropores (w = 1.36 nm) are investigated by small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) measurements between 20 K and 298 K. The SAXS results suggest that the density of the water in the micropores increased with increasing temperature over a wide temperature range (20-277 K). The density changed by 10%, which is comparable to the density change of 7% between bulk ice (I(c)) at 20 K and water at 277 K. The results of XRD at low temperatures (less than 200 K) show that the water forms the cubic ice (I(c)) structure, although its peak shape and radial distribution functions changed continuously to those of a liquid-like structure with increasing temperature. The SAXS and XRD results both showed that the water in the hydrophobic nanospaces had no phase transition point. The continuous structural change from ice I(c) to liquid with increasing temperature suggests that water shows negative thermal expansion over a wide temperature range in hydrophobic nanospaces. The combination of XRD and SAXS measurements makes it possible to describe confined systems in nanospaces with intermolecular structure and density of adsorbed molecular assemblies.