Correlation of the rotational and translational motions of methanol molecules in pure liquid methanol and in the presence of Li+ ions

Molecular dynamics computer simulations of liquid methanol (MeOH) and an infinitely dilute solution of Li⁺ ions in MeOH at a temperature of 298.15 K were performed. The time autocorrelation functions of the linear (translational) and angular (rotational) velocities and the rotational-translational cross-correlation functions (CCFs) for methanol molecules calculated in the molecular (moving) coordinates, as well as the corresponding spectral functions were analyzed. For bulk methanol, four nonzero of the nine possible CCFs were identified. A relationship between the positions of the peaks in the spectra of the CCFs studied and the spectra of hindered translations and librations of methanol molecules was revealed. It was demonstrated that the introduction of a lithium ion causes substantial changes in the nonzero CCFs for the first solvation shell of the ion but does not give rise to new rotational-translational correlations. The regularities obtained were interpreted in detail at the microscopic level with consideration given to the formation of hydrogen bonds in the solvent and to the anisotropy of intermolecular interactions.     

NEXAFS measurements of the molecular ordering in the boundary layers of liquid crystalline free standing films

By near edge X-ray absorption fine-structure (NEXAFS) spectroscopy a finite molecular tilt angle in the surface layer of a free standing film in the liquid crystalline smectic A phase of C7 was directly detected. Analysis of the angular dependent intensities of the oxygen K edge NEXAFS spectra leads to an average tilt angle of the molecules in the surface layer of about 34°, which is characteristic for the bulk smectic C* phase of C7.     

Molecular dynamics of n-hexane: a quasi-elastic neutron scattering study on the bulk and spatially nanochannel-confined liquid

We present incoherent quasi-elastic neutron scattering measurements in a wave vector transfer range from 0.4 A?(-1) to 1.6A? (-1) on liquid n-hexane confined in cylindrical, parallel-aligned nanochannels of 6 nm mean diameter and 260 μm length in monolithic, mesoporous silicon. They are complemented with, and compared to, measurements on the bulk system in a temperature range from 50 K to 250 K. The time-of-flight spectra of the bulk liquid (BL) can be modeled by microscopic translational as well as fast localized rotational, thermally excited, stochastic motions of the molecules. In the nano-confined state of the liquid, which was prepared by vapor condensation, we find two molecular populations with distinct dynamics, a fraction which is immobile on the time scale of 1 ps to 100 ps probed in our experiments and a second component with a self-diffusion dynamics slightly slower than observed for the bulk liquid. No hints of an anisotropy of the translational diffusion with regard to the orientation of the channels' long axes have been found. The immobile fraction amounts to about 5% at 250 K, gradually increases upon cooling and exhibits an abrupt increase at 160 K (20 K below bulk crystallization), which indicates pore freezing.     

盐对甲醇微观结构的影响

利用拉曼光谱研究盐对甲醇微观结构的影响.比较了不同盐/甲醇体系的O—H伸缩谱段和C—O伸缩谱段的超额拉曼光谱,对比给出了阴、阳离子与甲醇的相互作用.O—H伸缩谱段的超额拉曼光谱明显地显示了阴离子与甲醇形成弱氢键,氢键强度排序为CH3OH-CH3OHCl--CH3OHNO3--CH3OHClO4--CH3OH,在这个波段内,基本观察不到阳离子与甲醇的相互作用.在C—O伸缩谱段内,阴阳离子均有显著的体现,且与它们作用的甲醇C—O伸缩振动频率有如下的关系:CH3—OH(阴离子)CH3—OH(体相)CH3—OH(阳离子).根据C—O伸缩谱段的超额拉曼光谱,拟合了该谱段的拉曼光谱,由分解的谱峰强度得到阴、阳离子第一溶剂化层中甲醇分子的数目,结果显示在该浓度(～0.005)下离子对第一溶剂化层以外的甲醇氢键网络结构没有明显影响.     

Spectroscopic characterization of microscopic hydrogen-bonding disparities in supercritical water

The local hydrogen-bonding environment in supercritical water (380 degrees C, 300 bars, density 0.54 gcm3) was studied by x-ray Raman scattering at the oxygen K edge. The spectra are compared to those of the gas phase, liquid surface, bulk liquid, and bulk ice, as well as to calculated spectra. The experimental model systems are used to assign spectral features and to quantify specific local hydrogen-bonding situations in supercritical water. The first coordination shell of the molecules is characterized in more detail with the aid of the calculations. Our analysis suggests that approximately 65% of the molecules in supercritical water are hydrogen bonded in configurations that are distinctly different from those in liquid water and ice. In contrast to liquid water the bonded molecules in supercritical water have four intact hydrogen bonds and in contrast to ice large variations of bond angles and distances are observed. The remaining approximately 35% of the molecules exhibit two free O-H bonds and are thus either not involved in hydrogen bonding at all or have one or two hydrogen bonds on the oxygen side. We determine an average O-O distance of 3.1+/-0.1 A in supercritical water for the H bonded molecules at the conditions studied here. This and the corresponding hydrogen bond lengths are shown to agree with neutron- and x-ray-diffraction data at similar conditions. Our results on the local hydrogen-bonding environment with mainly two disparate hydrogen-bonding configurations are consistent with an extended structural model of supercritical water as a heterogeneous system with small patches of bonded molecules in various tetrahedral configurations and surrounding nonbonded gas-phase-like molecules.     

Computational study of ion distributions at the air/liquid methanol interface

Molecular dynamic simulations with polarizable potentials were performed to systematically investigate the distribution of NaCl, NaBr, NaI, and SrCl(2) at the air/liquid methanol interface. The density profiles indicated that there is no substantial enhancement of anions at the interface for the NaX systems, in contrast to what was observed at the air/aqueous interface. The surfactant-like shape of the larger more polarizable halide anions, which is part of the reason they are driven to air/aqueous interfaces, was compensated by the surfactant nature of methanol itself. These halide anions had on average an induced dipole of moderate magnitude in bulk methanol. As a consequence, methanol hydroxy groups donated hydrogen bonds to anions where the negatively charged side of the anion induced dipole pointed, and methyl groups interacted with anions where the positively charged side of the anion-induced dipole pointed. Furthermore, salts were found to disrupt the surface structure of methanol. For the neat air/liquid methanol interface, there is relative enhancement of methyl groups at the outer edge of the air/liquid methanol interface in comparison with hydroxy groups, but with the addition of NaX this enhancement was reduced somewhat. Finally, with the additional of salts to methanol, the computed surface potentials decreased, which is in contrast to what is observed in corresponding aqueous systems, where the surface potential increases with the addition of salts. Both of these trends have been indirectly observed with experiments. The surface potential trends were found to be due to the greater propensity of anions for the air/water interface that is not present at the air/liquid methanol interface.     

Structural Peculiarities of Water Solutions in <Emphasis Type="Italic">n</Emphasis>-Alkanols Derived from the Study of Bulk Properties at Different Temperatures

The structural behavior of water microimpurities in n-alkanols (C₁-C₇) is considered by using our and literature data on the bulk properties of infinitely dilute solutions of H₂O in the above organic solvents at 278.15 K, 298.15 K, and 318.15 K. Volume effects of water solution in hypothetical alkanols HOH (pseudowater) and H(CH₂)OH (pseudomethanol) with molar volumes corresponding to volume effects in water and methanol in pure liquid states have been evaluated. The behavior of water in methanol, which is distinct from the behavior of other H₂O—n-alkanol systems, is of configurational nature and is associated with the unique molecular structure of this alcohol (i.e., with the absence of hydrocarbon chains in its molecules) and also with steric peculiarities of the arrangement of solute molecules in the structural matrix of the solvent (so-called “edge effect”).Original Russian Text Copyright © 2004 by E. V. Ivanov, V. K. Abrosimov, and E. Yu. Lebedeva__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 862–869, September–October, 2004.     

The structure of water and methanol adsorbed on silica gel by FT-NIR spectroscopy

The NIR adsorption spectra were analyzed quantitatively on the fundamental, combination and first overtone region of OH vibrations of silanol groups, water and methanol adsorbed on mesoporous silica gels. Adsorbed methanol constitutes first layer of about 3 molecules/um^–2 and second layer, the structure of which is similar to that of bulk methanol liquid. Adsorbed water consists of a first layer of about 3 molecules/nm^–2, the second layer of about 9 molecules/nm^–2 and the third layer has a structure similar to the that of bulk water. The molecular configuration at the interface is discussed.     

Vibrational overtone spectroscopy of saturated hydrocarbons dissolved in liquefied Ar, Kr, Xe, and N2

This article presents a collection of vibrational overtone spectra of hydrocarbons in cryogenic solutions. Vibrational overtone spectra of ethane and propane dissolved in liquid argon and n-butane and isobutane dissolved in liquid krypton were recorded between 5000 and 14,000 cm(-1). Spectral regions for the first four overtones were measured using a Fourier transform spectrophotometer. The fifth overtone (Deltaupsilon = 6) spectra were recorded with a double beam (pump-probe) thermal lens technique using concentrations as low as 10-3 mole fraction. We obtained the C-H (Deltaupsilon = 6) spectra of (a) liquid ethane at 100 K and ethane in solutions in liquid Ar at 92 K and liquid N2 at 85 K, (b) liquid propane at 148 K and propane in liquid Ar at 93 K, (c) n-butane in liquid Kr at 129 K, (d) n-pentane in liquid Xe at 160 K, and (e) isobutane liquid at 135 K and isobutane in liquid Kr at 130 K. Local-mode parameters were calculated for primary, secondary, and tertiary C-H oscillators in solution and compared with gas-phase local-mode parameters. The peak frequency shift (Deltaomega) from gas phase to solution is explained by the change in harmonic frequency and anharmonicity in solution with respect to the gas-phase values. The bandwidth (Deltaomega1/2) of the (Deltaupsilon = 6) C-H absorption bands of ethane in solution can be explained in terms of collisions with the solvent molecules.     

Molecular dynamics simulation of liquid methanol. I. Molecular modeling including C-H vibration and Fermi resonance

A flexible and polarizable methanol model has been developed on the basis of charge response kernel (CRK) theory. The present CRK methanol model well reproduces bulk liquid and interfacial properties, including density, enthalpy of vaporization, diffusion coefficient, surface tension, and radial distribution functions. The modeling of intramolecular potential incorporates the anharmonic coupling effects pertinent to the Fermi resonance of stretching and bending overtones, with its effective quantum correction. Therefore, the present methanol model can describe the vibrational spectroscopic features of infrared, Raman, and sum frequency generation spectra of C-H or C-D stretching region of methanol or deuterated methanol on the same footing. This model allows for further detailed analysis of C-H vibrations of alkyl moieties by molecular dynamics simulation.     

Isotope effects in liquid water by infrared spectroscopy. IV. No free OH groups in liquid water

The presence of free OH (OH not H-bonded) in bulk water is a key element for the determination of its molecular structure. The OH covalent bond infrared (IR) absorption is highly sensitive to the molecular environment. For this reason, IR spectroscopy is used for the determination of free OH. A workable definition of this is obtained with methanol (MeOH) in hexane where minute quantities of free OH are present. These absorb at 3654?cm(-1) (a 27?cm(-1) redshift from the gas position) with a full width at half height of 35?cm(-1). The IR spectrum of water between room temperature and 95?°C does not display such a band near 3650?cm(-1). This indicates that we do not see, in the IR spectra, the "free" OH group. From this we conclude that it is not present in liquid water at least down to the 1000 ppm level which is the limit of detectivity of our spectrometer. Other spectroscopic considerations of methanol and water in acetonitrile solutions indicate that weak H-bonds are also not present in liquid water.     

Electronic structure of lithium nickel oxides by electron energy loss spectroscopy

The electronic structures of NiO, LiNiO2, and NiO2 are studied by the electron energy loss spectroscopy at Ni L(2,3), Ni M(2,3), and O K edges. The Ni L(2,3) edge spectra suggest that the formal charge of nickel is +2 in NiO, +3 with a low-spin state in LiNiO2, and +4 with a low-spin state in NiO2. This is well confirmed by first-principles calculations. The Ni M(2,3) edge spectra show similar chemical shifts to those of the Ni L(2,3) edge. Superposition of the Li K edge spectrum, however, hinders further analysis. Although the formal charge of oxygen is -2 in all the three phases, the O K edge spectra indicate a more remarkable difference in the electronic structure of the oxygen in NiO2 than that in either NiO or LiNiO2. The spectra suggest that lithium extraction from LiNiO2 reinforces the covalent bonding between the oxygen and nickel atoms and causes a notable reduction in electron density at the oxygen atoms.     

Investigations with infrared spectroscopy on films of the ionic liquid [EMIM]Tf2N

The reflection-absorption infrared (RAIRS) spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]Tf 2N) are presented as a function of temperature between 114 and 292 K. A comparison is made with the corresponding infrared spectra (obtained with transmission spectroscopy) from bulk [EMIM]Tf 2N. The liquid and amorphous films show rather similar spectra, indicating that the film structure is similar in both cases. On the other hand, these spectra differ considerably from those of crystalline films. Characteristic differences seen between the film and bulk spectra are attributed to the different structures of the respective networks. There are, however, indications that under all studied conditions the cation-anion interaction is between the C-H groups of the [EMIM] ring and the SO 2 groups of the anion.     

Far-infrared absorption of water clusters by first-principles molecular dynamics

Based on first-principle molecular dynamic simulations, we calculate the far-infrared spectra of small water clusters (H(2)O)(n) (n = 2, 4, 6) at frequencies below 1000 cm(-1) and at 80 K and at atmospheric temperature (T>200 K). We find that cluster size and temperature affect the spectra significantly. The effect of the cluster size is similar to the one reported for confined water. Temperature changes not only the shape of the spectra but also the total strength of the absorption, a consequence of the complete anharmonic nature of the classical dynamics at high temperature. In particular, we find that in the frequency region up to 320 cm(-1), the absorption strength per molecule of the water dimer at 220 K is significantly larger than that of bulk liquid water, while tetramer and hexamer show bulklike strengths. However, the absorption strength of the dimer throughout the far-infrared region is too small to explain the measured vapor absorption continuum, which must therefore be dominated by other mechanisms.     

Vapor—liquid equilibrium studies for the carbon dioxide—methanol system

Experimental vapor—liquid equilibrium measurements of carbon dioxide and methanol have been conducted from 230 K (−43.15°C) to 330 K (56.85°C) at pressures to the very vicinity of the critical states. The consistency of the data sets are examined and compared to literature values.Unlike the methane—methanol system, which exhibits two liquid phases at low temperatures, the carbon dioxide—methanol system exhibits complete liquid phase miscibility. Accordingly, the effects of critical behavior on the vapor liquid equilibria behavior begin to manifest themselves at much lower pressures.     

Structure of the liquid-vapor interface of water-methanol mixtures as seen from Monte Carlo simulations

Monte Carlo simulation of the vapor-liquid interface of water-methanol mixtures of different compositions, ranging from pure water to pure methanol, have been performed on the canonical (N, V, T) ensemble at 298 K. The analysis of the systems simulated has revealed that the interface is characterized by a double layer structure: methanol is strongly adsorbed at the vapor side of the interface, whereas this adsorption layer is followed at its liquid side by a depletion layer of methanol of lower concentration than in the bulk liquid phase of the system. The dominant feature of the interface has been found to be the adsorption layer in systems of methanol mole fractions below 0.2, and the depletion layer in systems of methanol mole fractions between 0.25 and 0.5. The orientation of the molecules located at the depletion layer is found to be already uncorrelated with the interface, whereas the methanol molecules of the adsorption layer prefer to align perpendicular to the interface, pointing straight toward the vapor phase by their methyl group. Although both the preference of the molecular plane for a perpendicular alignment with the interface and the preference of the methyl group for pointing straight to the vapor phase are found to be rather weak, the preference of the methyl group for pointing as straight toward the vapor phase as possible within the constraint imposed by the orientation of the molecular plane is found to be fairly strong. One of the two preferred orientations of the interfacial water molecules present in the neat system is found to disappear in the presence of methanol, because methanol molecules aligned in their preferred orientation can replace these water molecules in the hydrogen-bonding pattern of the interface.     

In situ ATR-IR spectroscopic and reaction kinetics studies of water-gas shift and methanol reforming on Pt/Al2O3 catalysts in vapor and liquid phases

Reaction kinetics measurements of the water-gas shift reaction were carried out at 373 K on Pt/Al2O3 in vapor phase to investigate the effects of CO, H2, and H2O partial pressures. Results of in situ ATR-IR studies conducted in vapor phase under similar conditions suggest that the Pt surface coverage by adsorbed CO is high (approximately 90% of the saturation coverage), leading to a negligible effect of the CO pressures on the rate of reaction. The negative reaction order with respect to the H2 pressure is caused by the increased coverage of adsorbed H atoms, and the fractional positive order with respect to the water pressure is consistent with non-equilibrated H2O dissociation on Pt. Results of in situ ATR-IR studies carried out at 373 K show that the presence of liquid water leads to a slight decrease in the Pt surface coverage by adsorbed CO (approximately 80% of the saturation coverage) when the CO partial pressure is the same as in the vapor-phase studies. The rate of the WGS reaction in the presence of liquid water is comparable to the rate under complete vaporization conditions when other factors (such as CO partial pressure) are held constant. Reaction kinetics measurements of methanol reforming were carried out at 423 K over a total pressure range of 1.36-5.84 bar. In situ ATR-IR studies were conducted at 423 K to determine the Pt surface coverage by adsorbed CO in completely vaporized methanol feeds and in aqueous methanol solutions. The decomposition of methanol is found to be slower during the reforming of methanol in liquid phase than in vapor phase, which leads to a lower rate of hydrogen production in liquid phase (0.08 min(-1) at 4.88 bar) than in vapor phase (0.23 min(-1) at 4.46 bar). The lower reaction order with respect to methanol concentration observed for vapor-phase versus liquid-phase methanol reforming (0.2 versus 0.8, respectively) is due to the higher extent of CO poisoning on Pt for reforming in vapor phase than in liquid phase, based on the higher coverage by adsorbed CO observed in completely vaporized methanol feeds (55-60% of the saturation coverage) than in aqueous methanol feed solutions (29-40% of the saturation coverage).     

丙酮+环己烷+甲醇组成的最低共沸混合物热力学性质的研究

Molar heat capacities of the pure samples of acetone,methanol and the azeotropic mixture composed of acetone,cyclohexane and methanol were measured by an adiabatic calorimeter from 78 to 320 K.The solid-solid andsolid-liquid phase transitions of the pure samples and the mixture were determined based on the curve of the heatcapacity with respect to temperature.The phase transitions took place at(126.16±0.68)and(178.96±1.47)K forthe sample of acetone,(157.79±0.95)and(175.93±0.95)K for methanol,which were corresponding to thesolid-solid and the solid-liquid phase transitions of the acetone and the methanol,respectively.And the phase tran-sitions occurred in the temperature ranges of 120 to 190 K and 278 to 280 K corresponding to the solid-solid andthe solid-liquid phase transitions of mixture of acetone,cyclohexane and methanol,respectively.The thermody-namic functions and the excess thermodynamic functions of the mixture relative to standard temperature of 298.15K were derived based on the relationships of the thermodynamic functions and the function of the measured heatcapacity with respect to temperature.     

Relation between solvent and protein dynamics as studied by dielectric spectroscopy

We present results obtained by dielectric spectroscopy in wide frequency (10(-2)-10(9) Hz) and temperature ranges on human hemoglobin in the three different solvents water, glycerol, and methanol, at a solvent level of 0.8 g of solvent/g of protein. In this broad frequency region, there are motions on several time-scales in the measured temperature range (110-370 K for water, 170-410 K for glycerol, and 110-310 K for methanol). For all samples, the dielectric data shows at least four relaxation processes, with frequency dependences that are well described by the Havriliak-Negami or Cole-Cole functions. The fastest and most pronounced process in the dielectric spectra of hemoglobin in glycerol and methanol solutions is similar to the alpha-relaxation of the corresponding bulk solvent (but shifted to slower dynamics due to surface interactions). For water solutions, however, this process corresponds to earlier results obtained for water confined in various systems and it is most likely due to a local beta-relaxation. The slowing down of the glycerol and methanol relaxations and the good agreement with earlier results on confined water show that this process is affected by the interaction with the protein surface. The second fastest process is attributed to motions of polar side groups on the protein, with a possible contribution from tightly bound solvent molecules. This process is shifted to slower dynamics with increasing solvent viscosity, and it shows a crossover in its temperature dependence from Arrhenius behavior at low temperatures to non-Arrhenius behavior at higher temperatures where there seems to be an onset of cooperativity effects. The origins of the two slowest relaxation processes (visible at high temperatures and low frequencies), which show saddlelike temperature dependences for the solvents water and methanol, are most likely due to motions of the polypeptide backbone and an even more global motion in the protein molecule.     

Catalytic Preparation of Methyl Formate from Methanol over Silver

A catalytic reaction over a silver catalyst performed in an unregarded temperature region（473-873 K） with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate（ca. 14. 8% ） with a selectivity 〉90% was obtained at about 573 K. Because α- oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over Oα -rich and Oγ-rich samples.