Structure and dynamics of aqueous NaCl solutions at high temperatures and pressures.

The structure of a concentrated solution of NaCl in D2O was investigated by in situ high-pressure neutron diffraction with chlorine isotope substitution to give site-specific information on the coordination environment of the chloride ion. A broad range of densities was explored by first increasing the temperature from 323 to 423 K at 0.1 kbar and then increasing the pressure from 0.1 to 33.8 kbar at 423 K, thus mapping a cyclic variation in the static dielectric constant of the pure solvent. The experimental work was complemented by molecular dynamics simulations using the TIP4P/2005 model for water, which were validated against the measured equation of state and diffraction results. Pressure-induced anion ordering is observed, which is accompanied by a dramatic increase in the Cl-O and O-O coordination numbers. With the aid of bond-distance resolved bond-angle maps, it is found that the increased coordination numbers do not originate from a sizable alteration to the number of either Cl⋯D-O or O⋯D-O hydrogen bonds but from the appearance of non-hydrogen-bonded configurations. Increased pressure leads to a marked decrease in the self-diffusion coefficients but has only a moderate effect on the ion-water residence times. Contact ion pairs are observed under all conditions, mostly in the form of charge-neutral NaCl0 units, and coexist with solvent-separated Na+-Na+ and Cl--Cl- ion pairs. The exchange of water molecules with Na+ adopts a concerted mechanism under ambient conditions but becomes non-concerted as the state conditions are changed. Our findings are important for understanding the role of extreme conditions in geochemical processes.

High-pressure transformation of SiO2 glass from a tetrahedral to an octahedral network: a joint approach using neutron diffraction and molecular dynamics.

A combination of in situ high-pressure neutron diffraction at pressures up to 17.5(5) GPa and molecular dynamics simulations employing a many-body interatomic potential model is used to investigate the structure of cold-compressed silica glass. The simulations give a good account of the neutron diffraction results and of existing x-ray diffraction results at pressures up to ~60 GPa. On the basis of the molecular dynamics results, an atomistic model for densification is proposed in which rings are "zipped" by a pairing of five- and/or sixfold coordinated Si sites. The model gives an accurate description for the dependence of the mean primitive ring size ⟨n⟩ on the mean Si-O coordination number, thereby linking a parameter that is sensitive to ordering on multiple length scales to a readily measurable parameter that describes the local coordination environment.