Solvation Properties of Neutral Gold Species in Supercritical Water Studied By THz Spectroscopy.

Supercritical water provides distinctly different solvation properties compared to what is known from liquid water. Despite its prevalence deep in the Earth's crust and its role in chemosynthetic ecosystems in the vicinity of hydrothermal vents, molecular insights into its solvation mechanisms are still very scarce compared to what is known for liquid water. Recently, neutral metal particles have been detected in hydrothermal fluids and proposed to explain the transport of gold species to ore deposits on Earth. Using ab initio molecular dynamics, we elucidate the solvation properties of small gold species at supercritical conditions. The neutral metal clusters themselves contribute enormous THz intensity not because of their intramolecular vibrations, but due to their pronounced electronic polarization coupling to the dynamical supercritical solvent, leading to a continuum absorption up to about 1000 cm-1. On top, long-lived interactions between the gold clusters and solvation water leads at these supercritical conditions to a sharp THz resonance that happens to be close to the one due to H-bonding in liquid water at ambient conditions. The resulting distinct resonances can be used to analyse the solvation properties of neutral metal particles in supercritical aqueous solutions.

Revealing the Molecular Origin of Anisotropy around Chloride Ions in Bulk Water.

A clear picture of the local solvation structure around halide anions in liquid water remains elusive. This discussion has been stimulated by pioneering simulation results that proposed a "hydrophobic cavity" around anions in the bulk, which is analogous to air at the air-water interface. However, there is also sound experimental and theoretical evidence that halide ions are rather symmetrically solvated in the bulk, leading to a different viewpoint. Using extensive ab initio molecular dynamics simulations of an aqueous Cl- solution, we indeed find an anisotropic arrangement of H-bonded versus interstitial water molecules. The latter are not H-bonded to the anions and thus do not couple much electronically to Cl-. The resulting purely electronic anisotropy of the local solvation environment correlates with that structural anisotropy, which however should not be understood as an empty cavity─as it would be at the air-water interface─but rather contains interstitial water molecules.

Spectroscopy from Machine Learning by Accurately Representing the Atomic Polar Tensor.

Vibrational spectroscopy is a key technique to elucidate microscopic structure and dynamics. Without the aid of theoretical approaches, it is, however, often difficult to understand such spectra at a microscopic level. Ab initio molecular dynamics has repeatedly proved to be suitable for this purpose; however, the computational cost can be daunting. Here, the E(3)-equivariant neural network e3nn is used to fit the atomic polar tensor of liquid water a posteriori on top of existing molecular dynamics simulations. Notably, the introduced methodology is general and thus transferable to any other system as well. The target property is most fundamental and gives access to the IR spectrum, and more importantly, it is a highly powerful tool to directly assign IR spectral features to nuclear motion─a connection which has been pursued in the past but only using severe approximations due to the prohibitive computational cost. The herein introduced methodology overcomes this bottleneck. To benchmark the machine learning model, the IR spectrum of liquid water is calculated, indeed showing excellent agreement with the explicit reference calculation. In conclusion, the presented methodology gives a new route to calculate accurate IR spectra from molecular dynamics simulations and will facilitate the understanding of such spectra on a microscopic level.

Nanoconfinement effects on water in narrow graphene-based slit pores as revealed by THz spectroscopy.

The properties of water at interfaces have long been known to differ from those of bulk water in many distinctive ways. More recently, specific confinement effects different from mere interfacial effects have been discovered upon enclosing water in very narrow cylindrical pores and planar surfaces as offered by nanotubes and slit pores, respectively. Using experimental and theoretical THz spectroscopy, we elucidate nanoconfinement effects on the H-bond network of stratified water lamellae that are hosted within graphene-based two-dimensional pores. Characteristic confinement-induced changes of the THz response are traced back to the level of structural dynamics, notably distinct resonances due to intralayer and interlayer H-bonds at correspondingly low and high intermolecular stretching frequencies and impact of dangling (free) OH bonds at the water-graphene interface that enormously broaden the librational band in sufficiently narrow pores. The interplay of these molecular effects causes characteristic changes of the THz lineshape upon nanoconfining water.

Nanosecond solvation dynamics of the hematite/liquid water interface at hybrid DFT accuracy using committee neural network potentials.

Metal oxide/water interfaces play an important role in biology, catalysis, energy storage and photocatalytic water splitting. The atomistic structure at these interfaces is often difficult to characterize by experimental techniques, whilst results from ab initio molecular dynamics simulations tend to be uncertain due to the limited length and time scales accessible. In this work, we train a committee neural network potential to simulate the hematite/water interface at the hybrid DFT level of theory to reach the nanosecond timescale and systems containing more than 3000 atoms. The NNP enables us to converge dynamical properties, not possible with brute-force ab initio molecular dynamics. Our simulations uncover a rich solvation dynamics at the hematite/water interface spanning three different time scales: picosecond H-bond dynamics between surface hydroxyls and the first water layer, in-plane/out-of-plane tilt motion of surface hydroxyls on the 10 ps time scale, and diffusion of water molecules from the oxide surface characterized by a mean residence lifetime of about 60 ps. Calculation of vibrational spectra confirm that H-bonds between surface hydroxyls and first layer water molecules are stronger than H-bonds in bulk water. Our study showcases how state of the art machine learning approaches can routinely be utilized to explore the structural dynamics at transition metal oxide interfaces with complex electronic structure. It foreshadows that c-NNPs are a promising tool to tackle the sampling problem in ab initio electrochemistry with explicit solvent molecules.

Supercritical Water is not Hydrogen Bonded.

Thinking about water is inextricably linked to hydrogen bonds, which are highly directional in character and determine the unique structure of water, in particular its tetrahedral H-bond network. Here, we assess if this common connotation also holds for supercritical water. We employ extensive ab initio molecular dynamics simulations to systematically monitor the evolution of the H-bond network mode of water from room temperature, where it is the hallmark of its fluctuating three-dimensional network structure, to supercritical conditions. Our simulations reveal that the oscillation period required for H-bond vibrations to occur exceeds the lifetime of H-bonds in supercritical water by far. Instead, the corresponding low-frequency intermolecular vibrations of water pairs as seen in supercritical water are found to be well represented by isotropic van-der-Waals interactions only. Based on these findings, we conclude that water in its supercritical phase is not a H-bonded fluid.

Assessing the properties of supercritical water in terms of structural dynamics and electronic polarization effects.

Supercritical water features fascinating physical properties which are fundamentally different compared to ambient liquid water. Importantly, it can gradually be compressed from gas-like to liquid-like densities while avoiding any thermodynamic phase transition. Although the interest in supercritical water has recently increased, many microscopic characteristics still remain unknown. Based on extensive ab initio molecular dynamics simulations using the RPBE-D3 density functional along a supercritical isotherm and the isochore from the ambient liquid into the supercritical phase, we provide a comprehensive picture of supercritical water regarding its structural, dynamical and electronic properties depending on the chosen thermodynamic state point. Our results do not only show that the effective molecular dipole moment of water can be gradually tuned as a function of density along an isotherm, but also that it correlates linearly with the number of H-bond neighbors all the way from liquid-like to gas-like densities which is shown to be caused by many-body electronic polarization and charge transfer effects. Remarkably, these polarization and charge transfer effects are still present even at rather low gas-like densities. Regarding the dynamics, the H-bond lifetime is largely decreased in supercritical water and follows an Arrhenius-type behavior as a function of temperature, while it is essentially unaffected by the extreme density changes along the supercritical isotherm. In contrast, the self-diffusion coefficient dramatically varies as a function of density along the isotherm, while it scales essentially linearly as a function of temperature along the isochore.

Terahertz Spectra of Microsolvated Ions: Do They Reveal Bulk Solvation Properties?

Complementing mid-infrared (mid-IR) spectroscopy mainly in the OH stretching region, liquid-state far-IR spectroscopy is successful in elucidating the properties of aqueous solutions by providing direct access to the hallmark of H-bonding at terahertz (THz) frequencies, namely, the H-bond network peak of water at roughly 200 cm-1 and its modifications in the hydration shells around solutes. Here, the idea is scrutinized whether ion hydration can be understood by studying the THz regime of "small" ion-water clusters in the gas phase as a function of size with subsequent extrapolation to the bulk limit. Our ab initio simulations of Na+(H2O) n clusters followed by rigorous decomposition of their THz response demonstrate that the 200 cm-1 network peak is suppressed even at n = 20 in the gas phase, yet it emerges when transferring ion-water complexes as small as n = 7 out of the liquid into vacuum. The underlying physical reason is not missing electronic polarization or charge-transfer effects in the gas phase, but rather the distinctly different structural dynamics of finite ion-water clusters in the gas phase compared to ion-water complexes of the same size in the liquid phase.

Investigation concerning the uniqueness of separatrix lines separating liquidlike from gaslike regimes deep in the supercritical phase of water with a focus on Widom line concepts.

The supercritical phase of fluids has long been known to feature significantly different liquidlike and gaslike regimes. However, it is textbook knowledge that the supercritical state is a homogeneous fluid phase where properties change continuously. Nevertheless, there has been an increasing amount of evidence published that suggests that there might exist a unique line that rigorously separates different regimes in supercritical phases, particularly in the case of water. Here, we use the quasiexact IAPWS95 equation of state to rigorously assess the macroscopic thermodynamic properties of supercritical water without invoking any water model or related approximations. We focus on how these properties change deep in the supercritical phase, in particular if they allow one to introduce a unique "thermodynamic separatrix." Our rigorous thermodynamic analysis, which relies exclusively on accurate experimental data, makes clear that there is no unique separatrix in real supercritical water-such as the recently much-invoked "Widom line." A comparison to the van der Waals equation of state reproduces qualitatively all our findings for real water, thereby suggesting that our analysis should be transferable to other fluids and critical points. Topological analysis of the H-bond network structure of supercritical water, as obtained from molecular-dynamics simulations using a standard water model, demonstrates that also the percolation line does not provide a meaningful separatrix to rigorously distinguish liquidlike from gaslike regimes.

Liquid-Vapor Phase Diagram of RPBE-D3 Water: Electronic Properties along the Coexistence Curve and in the Supercritical Phase.

On the basis of ab initio Gibbs ensemble Monte Carlo simulations, we map the liquid-vapor phase diagram of water described by the RPBE density functional supplemented by D3 dispersion corrections and estimate the critical point by density extrapolation. Knowing the approximate location of the critical point, two sets of ab initio molecular dynamics simulations at gas-like and liquid-like densities deep in the supercritical phase of water are carried out where particular attention is payed to ergodic sampling in view of large correlation lengths and long correlation times. Structural, H-bonding, and dipolar properties of RPBE-D3 water are analyzed along the liquid-vapor coexistence curve upon moving toward the critical point and compared to those in the supercritical state. The properties of high-density supercritical water are astonishingly similar to those of the liquid on the coexistence curve under subcritical conditions at comparable density. Upon decomposing the molecular dipole moments into purely configurational and electronic polarization/charge-transfer contributions, it is demonstrated that the latter play a decreasing role in liquid water upon approaching the critical point on the coexistence curve. Moreover, these many-body effects are systematically suppressed in supercritical water due to the significantly reduced H-bonding network.

Correlations in the Solute-Solvent Dynamics Reach Beyond the First Hydration Shell of Ions.

While the real-space structure of solvation shells has been explored for decades, a dynamical perspective that directly relies on changes in the H-bond network became accessible more recently mainly via far-infrared (THz) spectroscopies. A remaining key question is how many hydration shells are affected by ion-induced network perturbations. We disclose that theoretical THz difference spectra of aqueous salt solutions can be deciphered in terms of only a handful of dipolar auto- and cross-correlations, including the second solvation shell. This emphasizes the importance of cross-correlations being often neglected in multicomponent models. Analogously, experimental THz responses of simple ions can be deciphered in a similar way. Dramatic intensity cancellations due to large positive and negative contributions are found to effectively shift intensity maxima. Thus, THz spectroscopy provides an unprecedented view on the details of hydration dynamics, which can be understood by a combination of experiment and theory.