Effective force field for liquid hydrogen fluoride from ab initio molecular dynamics simulation using the force-matching method

A recently developed force-matching method for obtaining effective force fields for condensed matter systems from ab initio molecular dynamics (MD) simulations has been applied to fit a simple nonpolarizable two-site pairwise force field for liquid hydrogen fluoride. The ab initio MD in this case was a Car-Parrinello (CP) MD simulation of 64 HF molecules at nearly ambient conditions within the Becke-Lee-Yang-Parr approximation to the electronic density functional theory. The force-matching procedure included a fit of short-ranged nonbonded forces, bonded forces, and atomic partial charges. The performance of the force-match potential was examined for the gas-phase dimer and for the liquid phase at various temperatures. The model was able to reproduce correctly the bent structure and energetics of the gas-phase dimer, while the results for the structural properties, self-diffusion, vibrational spectra, density, and thermodynamic properties of liquid HF were compared to both experiment and the CP MD simulation. The force-matching model performs well in reproducing nearly all of the liquid properties as well as the aggregation behavior at different temperatures. The model is computationally cheap and compares favorably to many more computationally expensive potential energy functions for liquid HF.     

Ab initio molecular-dynamics simulation of aqueous proton solvation and transport revisited

The solvation and transport of the hydrated excess proton is studied using the Car-Parrinello molecular-dynamics (CPMD) simulation method. The simulations were performed using BLYP and HCTH gradient-corrected exchange-correlation energy functionals. The fictitious electronic mass was chosen to be small enough so that the underlying water structural and dynamical properties were converged with respect to this important CPMD simulation parameter. An unphysical overstructuring of liquid water in the CPMD simulations using the BLYP functional resulted in the formation of long-lived hydrogen-bonding structures involving the excess proton and a particular (special) water oxygen. The excess proton was observed to be attracted to the special oxygen through the entire length of the BLYP CPMD simulations. Consequently, the excess proton diffusion was limited by the mobility of the special oxygen in the slowly diffusing water network and, in turn, the excess proton self-diffusion coefficient was found to be significantly below the experimental value. On the other hand, the structural properties of liquid water in the HCTH CPMD simulation were seen to be in better agreement with experiment, although the water and excess proton diffusions were still well below the experimental value.     

Potentiometric studies of dithiooxamide with a sulphide-selective membrane electrode

The sulphide-selective electrode is applicable to the determination of dithiooxamide by titration with silver nitrate. The effect of the alkali content of the solutions on the reaction has been studied. The reaction products are silver sulphide, oxalic acid, and nitric acid. If the alkali concentration of the solution is lower than that equivalent to the acid formed during the titration, the amount of sulphide produced by hydrolysis decreases and the equilibrium potential is established more slowly.The determination is rapid and accurate in the presence of 1 M sodium hydroxide.     

Coordination polymers. VIII. IR spectroscopic studies on the mechanism of the reaction between polyesters and zinc oxide

This article was written for the purpose of investigating the mechanisms of reactions between unsaturated polyester resins and base anhydridelike metal oxides (CaO, MgO, ZnO) which cause an increase in viscosity. As a model system ethyl-hydrogen-succinate (ESH) and ZnO were reacted in CCl₄ and complexes that contained Zn-hydroxocarboxylate units took an essential part in this reaction. Solubility measurements of the model compounds and infrared (IR) spectra of the reaction products led to the conclusion that further molecular associates were formed from the mixed metal-hydroxocarboxylate complex by the carbonyl oxygens of ester groups, which resulted in end products of polymeric structure. It is suggested by IR spectroscopical analogies between the model compounds and reaction products of an adipic acid/butanediol-1,4 polyester with ZnO that similar reactions can account for the polyesters as well.     

Fast centroid molecular dynamics: a force-matching approach for the predetermination of the effective centroid forces

A fast centroid molecular dynamics (CMD) methodology is proposed in which the effective centroid forces are predetermined through a force-matching algorithm applied to a standard path integral molecular dynamics simulation. The resulting method greatly reduces the computational cost of generating centroid trajectories, thus extending the applicability of CMD. The method is applied to the study of liquid para-hydrogen at two state points and liquid ortho-deuterium at one state point. The static and dynamical results are compared to those obtained from full adiabatic CMD simulations and found to be in excellent agreement for all three systems; the transport properties are also compared to experiment and found to have a similar level of agreement.     

Electronic absorption spectra of the cations and anions formed from pyrrole analogs of the chalcones

The electronic absorption spectra of 29 pyrrole analogs of the chalcones have been studied in solutions of strong acids and alkalies, in which the corresponding cations and anions are formed. It has been shown by means of the IR spectra that the protonation of the pyrrole chalcones takes place at the carbonyl group. Considerations are given of the structure of the organic cations and anions studied and of the characteristic features in the change in their coloration as a function of their chemical structure. Satisfactory correlations have been found between the shift of the absorption frequency of the long-wave band which takes place at the transition from a neutral solution (molecules) to an acid solution (cations) or to an alkaline solution (anions) and Hammett's o constants. Three 3-(4-halophenyl)-1-(2-pyrryl)propenones not previously reported in the literature have been synthesized.     

Investigation of ion-selective electrodes based on quanternary phosphonium salts: Part 3. An Ion-Selective Electrode for Hexafluorophosphate

A hexafluorophosphate-selective electrode based on the tetradecylphosphonium hexafluorophosphate(V) ion-pair complex in a PVC membrane is described. The active material is a white powder; its solution in dibutyl phthalate was used for the electrode membranes. The composition of the tetradecylphosphonium hexafluorophosphate was identified as its infrared and ³¹P-n.m.r. spectra. The calibration curves for the elelctrode were investigated and interpreted with respect to the hydrogen fluoride concentration of the sample solution. It is shown that the hydrolysis of hexafluorophosphate depends on the hydrofluoric acid content of the solution. The lifetime of the electrodes is about one month and the limits of detection vary from aobut 10^?7 mol 1^?1 to 10^?6 mol 1^?1 with 0–1 mol 1^?1 hydrofluoric acid present.     

Structure and photoluminescence of the a-GexSe1−x system

GeGe like-bonds are formed in as-deposited films at x < 0.33 i.e. they are both chemically and structurally disordered. Photoluminescence (PL) intensity along with the fatigue of PL is presumably controlled by the positions of the demarcation levels which are displaced by changing the concentrations and cross sections of the recombination centres. The increase of Se content in these binary alloys leads to an increase of the concentration of non-radiative recombination centres. During fatigue both new centres are created and the cross sections of the pre-existing ones are changed.     

Electronic and vibrational spectra of chalcone analogs derived from 4- and 5-nitropyrroles

The electronic absorption spectra of ten chalcone analogs derived from 4- and 5-nitropyrroles have been measured in solution in ethanol, dioxane, concentrated sulfuric acid, and 20% ethanolic caustic potash and interpreted. The IR spectra of these compounds and also of 4- and 5-nitro-2-acetylpyrroles and 5-nitropyrrole-2-aldehyde have been measured in the 3700-500 cm^–1 region, an assignment of frequencies has been carried out, and considerations have been put forward on the connection between the characteristic features of the absorption and the chemical structure.