Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion–ion interactions are included at the centre of a Mie core; the ion–water interactions are also modelled with a Mie potential without an explicit treatment of ion–dipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion–ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion–solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimation. The inclusion of the Born free-energy contribution, together with appropriate estimates for the size of the ionic cavity, allows for accurate predictions of the Gibbs free energy of solvation of the ionic species considered. The solubility limits are also predicted for a number of salts; in cases where reliable reference data are available the predictions are in good agreement with experiment

Exploration of dynamical regimes of irradiated small protonated water clusters

We explore from a theoretical perspective the dynamical response of small water clusters, (H$_2$O)$_n$H$_3$O$^+$ with $n=1,2,3$, to a short laser pulse for various frequencies, from infrared (IR) to ultra-violet (UV) and intensities (from $6\times10^{13}$ W/cm$^2$ to $5\times10^{14}$ W/cm$^2$). To that end, we use time-dependent local-density approximation for the electrons, coupled to molecular dynamics for the atomic cores (TDLDA-MD). The local-density approximation is augmented by a self-interaction correction (SIC) to allow for a correct description of electron emission. For IR frequencies, we see a direct coupling of the laser field to the very light H$^+$ ions in the clusters. Resonant coupling (in the UV) and/or higher intensities lead to fast ionization with subsequent Coulomb explosion. The stability against Coulomb pressure increases with system size. Excitation to lower ionization stages induced strong ionic vibrations. These maintain rather harmonic pattern in spite of the sizeable amplitudes (often 10% of the bond length).Comment: accepted in Eur. J. Phys.

Microscopic dynamics of charge separation at the aqueous electrochemical interface

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na$^+$I$^-$, or classical ions, and the products of water autoionization, H$_3$O$^+$OH$^-$, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. Despite this, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free energy barrier to charge separation and a smaller flux over that barrier at the interface, results in a rate of dissociation that is 40x slower relative to the bulk. For water ions, a slightly higher free energy barrier is offset by a higher flux over the barrier from longer lived hydrogen bonding patters at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface.Comment: 6 pages, 3 figures + S

Ambidentate coordination in hydrogen bonded dimethyl sulfoxide, (CH3)2SOH3O+, and in dichlorobis(dimethyl sulfoxide) palladium(II) and platinum(II) solid solvates, by vibrational and sulfur K-edge X-ray absorption spectroscopy

The strongly hydrogen bonded species (CH3)(2)SO center dot center dot center dot H3O+ formed in concentrated hydrochloric acid displays a new low energy feature in its sulfur K-edge X-ray absorption near edge structure (XANES) spectrum. Density Functional Theory-Transition Potential (DFT-TP) calculations reveal that the strong hydrogen bonding decreases the energy of the transition S(1s) -> LUMO, which has antibonding sigma*(S-O) character, with about 0.8 eV. Normal coordinate force. field analyses of the vibrational spectra show that the SO stretching force constant decreases from 4.72 N cm(-1) in neat liquid dimethyl sulfoxide to 3.73 N cm(-1) for the hydrogen bonded (CH3)(2)SO center dot center dot center dot H3O+ species. The effects of sulfur coordination on the ambidentate dimethyl sulfoxide molecule were investigated for the trans-Pd((CH3)(2)SO)(2)Cl-2, trans-Pd((CD3)(2)SO)(2)Cl-2 and cis-Pt((CH3)(2)SO)(2)Cl-2 complexes with square planar coordination of the chlorine and sulfur atoms. The XANES spectra again showed shifts toward low energy for the transition S(1 s) -> LUMO, now with antibonding sigma*(M-Cl, M-S) character, with a larger shift for M = Pt than Pd. DFT-TP calculations indicated that the differences between the XANES spectra of the geometrical cis and trans isomers of the M((CH3)(2)SO)(2)Cl-2 complexes are expected to be too small to allow experimental distinction. The vibrational spectra of the palladium(II) and platinum(II) complexes were recorded and complete assignments of the fundamentals were achieved. Even though the M-S bond distances are quite similar the high covalency especially of the Pt-S bonds induces significant increases in the S-O stretching force constants, 6.79 and 7.18 N cm(-1), respectively

Chemical evolution of turbulent protoplanetary disks and the Solar nebula

This is the second paper in a series where we study the influence of transport processes on the chemical evolution of protoplanetary disks. Our analysis is based on a flared alpha-model of the DM Tau system, coupled to a large gas-grain chemical network. To account for production of complex molecules, the chemical network is supplied with an extended set of surface reactions and photo-processes in ice mantles. Our disk model covers a wide range of radii, 10-800 AU (from a Jovian planet-forming zone to the outer disk edge). Turbulent transport of gases and ices is implicitly modeled in full 2D along with the time-dependent chemistry. Two regimes are considered, with high and low efficiency of turbulent mixing. The results of the chemical model with suppressed turbulent diffusion are close to those from the laminar model, but not completely. A simple analysis for the laminar chemical model to highlight potential sensitivity of a molecule to transport processes is performed. It is shown that the higher the ratio of the characteristic chemical timescale to the turbulent transport timescale for a given molecule, the higher the probability that its column density will be affected by diffusion. We find that turbulent transport enhances abundances and column densities of many gas-phase species and ices, particularly, complex ones. For such species a chemical steady-state is not reached due to long timescales associated with evaporation and surface photoprocessing and recombination. In contrast, simple radicals and molecular ions, which chemical evolution is fast and proceeds solely in the gas phase, are not much affected by dynamics. All molecules are divided into three groups according to the sensitivity of their column densities to the turbulent diffusion. [Abridged]Comment: 42 pages, 13 figures, 16 tables, accepted for publication in ApJS

Spatially extended OH+ emission from the Orion Bar and Ridge

We report the first detection of a Galactic source of OH+ line emission: the Orion Bar, a bright nearby photon-dominated region. Line emission is detected over ~1' (0.12 pc), tracing the Bar itself as well as the Southern tip of the Orion Ridge. The line width of ~4 km/s suggests an origin of the OH+ emission close to the PDR surface, at a depth of A_V ~0.3-0.5 into the cloud where most hydrogen is in atomic form. Steady-state collisional and radiative excitation models require unrealistically high OH+ column densities to match the observed line intensity, indicating that the formation of OH+ in the Bar is rapid enough to influence its excitation. Our best-fit OH+ column density of ~1x10^14 cm^-2 is similar to that in previous absorption line studies, while our limits on the ratios of OH+/H2O+ (>~40) and OH+/H3O+ (>~15) are higher than seen before. The column density of OH+ is consistent with estimates from a thermo-chemical model for parameters applicable to the Orion Bar, given the current uncertainties in the local gas pressure and the spectral shape of the ionizing radiation field. The unusually high OH+/H2O+ and OH+/H3O+ ratios are probably due to the high UV radiation field and electron density in this object. In the Bar, photodissociation and electron recombination are more effective destroyers of OH+ than the reaction with H2, which limits the production of H2O+. The appearance of the OH+ lines in emission is the result of the high density of electrons and H atoms in the Orion Bar, since for these species, inelastic collisions with OH+ are faster than reactive ones. In addition, chemical pumping, far-infrared pumping by local dust, and near-UV pumping by Trapezium starlight contribute to the OH+ excitation. Similar conditions may apply to extragalactic nuclei where OH+ lines are seen in emission.Comment: Accepted by A&A; 10 pages, 5 figure

Interstellar Hydrides

Interstellar hydrides -- that is, molecules containing a single heavy element atom with one or more hydrogen atoms -- were among the first molecules detected outside the solar system. They lie at the root of interstellar chemistry, being among the first species to form in initially-atomic gas, along with molecular hydrogen and its associated ions. Because the chemical pathways leading to the formation of interstellar hydrides are relatively simple, the analysis of the observed abundances is relatively straightforward and provides key information about the environments where hydrides are found. Recent years have seen rapid progress in our understanding of interstellar hydrides, thanks largely to far-IR and submillimeter observations performed with the Herschel Space Observatory. In this review, we will discuss observations of interstellar hydrides, along with the advanced modeling approaches that have been used to interpret them, and the unique information that has thereby been obtained.Comment: Accepted for publication in Annual Review of Astronomy and Astrophysics 2016, Vol. 5