Ethylene glycol revisited: Molecular dynamics simulations and visualization of the liquid and its hydrogen-bond network.

Molecular dynamics simulations of liquid ethylene glycol described by the OPLS-AA force field were performed to gain insight into its hydrogen-bond structure. We use the population correlation function as a statistical measure for the hydrogen-bond lifetime. In an attempt to understand the complicated hydrogen-bonding, we developed new molecular visualization tools within the Vish Visualization shell and used it to visualize the life of each individual hydrogen-bond. With this tool hydrogen-bond formation and breaking as well as clustering and chain formation in hydrogen-bonded liquids can be observed directly. Liquid ethylene glycol at room temperature does not show significant clustering or chain building. The hydrogen-bonds break often due to the rotational and vibrational motions of the molecules leading to an H-bond half-life time of approximately 1.5 ps. However, most of the H-bonds are reformed again so that after 50 ps only 40% of these H-bonds are irreversibly broken due to diffusional motion. This hydrogen-bond half-life time due to diffusional motion is 80.3 ps. The work was preceded by a careful check of various OPLS-based force fields used in the literature. It was found that they lead to quite different angular and H-bond distributions.

On quantitative determination of volatile organic compound concentrations using proton transfer reaction time-of-flight mass spectrometry.

Proton transfer reaction - mass spectrometry (PTR-MS) has become a reference technique in environmental science allowing for VOC monitoring with low detection limits. The recent introduction of time-of-flight mass analyzer (PTR-ToF-MS) opens new horizons in terms of mass resolution, acquisition time, and mass range. A standard procedure to perform quantitative VOC measurements with PTR-ToF-MS is to calibrate the instrument using a standard gas. However, given the number of compounds that can be simultaneously monitored by PTR-ToF-MS, such a procedure could become impractical, especially when standards are not readily available. In the present work we show that, under particular conditions, VOC concentration determinations based only on theoretical predictions yield good accuracy. We investigate a range of humidity and operating conditions and show that theoretical VOC concentration estimations are accurate when the effect of water cluster ions is negligible. We also show that PTR-ToF-MS can successfully be used to estimate reaction rate coefficients between H(3)O(+) and VOC at PTR-MS working conditions and find good agreement with the corresponding nonthermal theoretical predictions. We provide a tabulation of theoretical rate coefficients for a number of relevant volatile organic compounds at various energetic conditions and test the approach in a laboratory study investigating the oxidation of alpha-pinene.

Contribution of filtration and photocatalysis to DOM removal and fouling mechanism during in-situ UV-LED photocatalytic ceramic membrane process.

The use of ceramic membranes and ultraviolet light-emitting diodes (UV-LEDs) has advanced the application of photocatalytic membrane for water treatment. We systematically evaluated the contribution of filtration and photocatalysis to dissolved organic matter (DOM) removal and fouling mechanism during in-situ UV-LED photocatalytic ceramic membrane filtration. The results showed that physical rejection primarily led to removal of 4-15 kDa molecules and photocatalysis further increased the removal of 1-4 kDa molecules, causing small sized microbial humic-like or protein-like materials in the permeate. In-situ UV-LED photocatalysis had an excellent effect on membrane fouling mitigation regardless of DOM sources. The dominant fouling mechanism changed from partial blockage to gel layer formation with increasing Ca2+ concentration but did not change with UV treatment. Correlation analysis revealed that the removal of 1-4 kDa molecules contributed to the mitigation of both reversible and irreversible fouling resistance, and the small molecules were the major cause of irreversible fouling resistance. Removal of 1-4 kDa terrestrial humic acid-like contributed to the pore blockage mechanism for synthetic water. Removal of 4-15 kDa protein-like materials was closely correlated to the pore blockage mechanism for real water. Trihalomethanes (THMs) and haloacetic acids (HAAs) formation potential (FP) were both significantly reduced after photocatalytic ceramic membrane process, but precursors of nitrogenous disinfection by-products (N-DBPs) with high toxicity were not removed by filtration or by photocatalysis, which deserves attention. Membrane rejection made higher contribution to better DBPFP control than photocatalysis. This study provides novel insights into the impact of UV-LED on DOM removal, DBPFP control and fouling mitigation, promoting the development of photocatalytic ceramic membrane filtration.

Pressure-Induced Enhanced Optical Absorption in Sulvanite Compound Cu3TaX4 (X = S, Se, and Te): An ab Initio Study.

Ab initio study on the family of ternary copper chalcogenides Cu3TaX4 (X = S, Se, and Te) is performed to investigate the suitability of these compounds to applications as photovoltaic absorber materials. The density functional theory based full potential linearized augmented plane wave method (FP-LAPW method) is employed for computational purposes. The electronic structure and optical properties are determined including electron-electron interaction and spin-orbit coupling (SOC), within the generalized gradient approximation plus Hubbard U (GGA+U) and GGA+U+SOC approximation. The large optical band gaps of Cu3TaS4 and Cu3TaSe4 considered ineffective for absorber materials, and also the hole effective mass has been modulated through applied pressure. These materials show extreme resistance to external pressure, and are found to be stable up to a pressure range of 10 GPa, investigated using phonon dispersion calculations. The observed optical properties and the absorption coefficients within the visible-light spectrum make these compounds promising materials for photovoltaic applications. The calculated energy and optical band gaps are consistent with the available literature and are compared with the experimental results where available.

Structural and Optical Characteristics of Aqueous Solutions of Acetic Acid.

A refractometric method, coupled with molecular dynamics study, attenuated total reflection Fourier transform infrared (ATR FT-IR), and Raman spectroscopy, was used to determine optical characteristics of concentration features of aqueous solutions of acetic acid. Measurements of the refractive index of aqueous solutions of acetic acid in the wide range of acetic acid concentrations (∼ 0 ÷ 1 mole fraction) in a solution at a room temperature were conducted. Maximum value of refractive index was detected at a concentration of ∼0.3 mole fraction. The deviation from the parabolic form of the dependence of the refractive index on the concentration occurs at a concentration of ∼0.8 mole fraction. As far as we know, this deviation has been observed for the first time. The maximum is attributed to the largest number of molecular interactions between water and acetic acid molecules, while the deviation is associated with the parallel orientation of acetic acid molecules. To identify the reconstructing of molecules in the system, FT-IR and Raman spectra of these solutions at a concentration of ∼0.3 and ∼0.8 mole fraction were recorded and compared with pure solutions. The data obtained by using ATR FT-IR and Raman spectroscopy support the idea that the refractometric method is sensitive to determine the structural states of aqueous solutions of acetic acid.

Interfacial bond-breaking electron transfer in mixed water-ethylene glycol solutions: reorganization energy and interplay between different solvent modes.

We explore solvent dynamics effects in interfacial bond breaking electron transfer in terms of a multimode approach and make an attempt to interpret challenging recent experimental results (the nonmonotonous behavior of the rate constant of electroreduction of S2O8(2-) from mixed water-EG solutions when increasing the EG fraction; see Zagrebin, P.A. et al. J. Phys. Chem. B 2010, 114, 311). The exact expansion of the solvent correlation function (calculated using experimental dielectric spectra) in a series predicts the splitting of solvent coordinate in three independent modes characterized by different relaxation times. This makes it possible to construct a 5D free-energy surface along three solvent coordinates and one intramolecular degree of freedom describing first electron transfer at the reduction of a peroxodisulphate anion. Classical molecular dynamics simulations were performed to study the solvation of a peroxodisulphate anion (S2O8(2-)) in oxidized and reduced states in pure water and ethylene glycol (EG) as well as mixed H2O-EG solutions. The solvent reorganization energy of the first electron-transfer step at the reduction of S2O8(2-) was calculated for several compositions of the mixed solution. This quantity was found to be significantly asymmetric. (The reorganization energies of reduction and oxidation differ from each other.) The averaged reorganization energy slightly increases with increasing the EG content in solution. This finding clearly indicates that for the reaction under study the static solvent effect no longer competes with solvent dynamics. Brownian dynamics simulations were performed to calculate the electron-transfer rate constants as a function of the solvent composition. The results of the simulations explain the experimental data, at least qualitatively.