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.

Anisotropic pressure effects on nanoconfined water within narrow graphene slit pores.

There is an increasing interest toward disclosing and explaining confinement effects on liquids, such as water or aqueous solutions, in slit pore setups. Particularly puzzling are the changes of physical and chemical properties in the nanoconfinement regime where no bulk-like water phase exists between the two interfacial water layers such that the density profile across the slit pore becomes highly stratified, ultimately leading to bilayer and monolayer water. These changes must be quantified with respect to some meaningful reference state of water, the most natural one being bulk water at the same pressure and temperature conditions. However, bulk water is a homogeneous liquid with isotropic properties, whereas water confined in slit pores is inhomogeneous, implying anisotropic properties as described by the perpendicular and parallel components of the respective tensors. In the case of pressure, the inhomogeneous nature of the setup results in a well-defined difference between the perpendicular and parallel pressure tensor components that is uniquely determined by the interfacial tension being a thermodynamic property. For bilayer water constrained in graphene slit pores that are only about 1 nm wide, we demonstrate that there exists a thermodynamic point where the pressure tensor of the inhomogeneous fluid, nanoconfined water, is effectively isotopic and the pressure is thus scalar as in the homogeneous fluid, bulk water. This specific point of vanishing effective interfacial tension is proposed to serve as a well-defined reference state to compare the properties of nanoconfined liquids to those of the corresponding bulk liquid at the same (isotropic) pressure and temperature conditions. In future work, this idea could be applied to assess confinement effects on chemical reactivity in aqueous solutions as well as to other nanoconfined liquids in other pores such as layered minerals.

Elucidating the Self-cleavage Dynamics of Hairpin Ribozyme by Mode-decomposed Infrared Spectroscopy.

While catalytic reactions of biomolecular processes play an indispensable role in life, extracting the underlying molecular picture often remains challenging. Based on ab initio simulations of the self-cleavage reaction of hairpin ribozyme, mode-decomposed infrared spectra, and cosine similarity analysis to correlate the product with reactant IR spectra, we demonstrate a strategy to extract molecular details from characteristic spectral changes. Our results are in almost quantitative agreement with the experimental IR band library of nucleic acids and suggest that the spectral range of 800-1200 cm-1 is particularly valuable to monitor self-cleavage. Importantly, the cosine similarities also disclose that IR peaks subject to slight shifts due to self-cleavage might be unrelated, while strongly shifting resonances can correspond to the same structural dynamics. This framework of correlating complex IR spectra at the molecular level along biocatalytic reaction pathways is broadly applicable.

Coupled Cluster Molecular Dynamics of Condensed Phase Systems Enabled by Machine Learning Potentials: Liquid Water Benchmark.

Coupled cluster theory is a general and systematic electronic structure method, but in particular the highly accurate "gold standard" coupled cluster singles, doubles and perturbative triples, CCSD(T), can only be applied to small systems. To overcome this limitation, we introduce a framework to transfer CCSD(T) accuracy of finite molecular clusters to extended condensed phase systems using a high-dimensional neural network potential. This approach, which is automated, allows one to perform high-quality coupled cluster molecular dynamics, CCMD, as we demonstrate for liquid water including nuclear quantum effects. The machine learning strategy is very efficient, generic, can be systematically improved, and is applicable to a variety of complex systems.

Internal Electric Field-Induced Formation of Exotic Linear Acetonitrile Chains.

The application of external electric and magnetic fields is a powerful tool for aligning molecules in a controlled way, if the thermal fluctuations are small. Here we demonstrate that the same holds for internal electric fields in a molecular cluster. The electric field of a single molecular dipole, HCl, is used to manipulate the aggregation mechanism of subsequently added acetonitrile molecules. As a result, we could form exotic linear acetonitrile (CH3CN) chains at 0.37 K, as confirmed by infrared spectroscopy in superfluid helium nanodroplets. These linear chains are not observed in the absence of HCl and can be observed only when the internal electric field created by an HCl molecule is present. The accompanying simulations provide mechanistic insights into steric control, explain the selectivity of the process, and show that non-additive electronic polarization effects systematically enhance the dipole moment of these linear chains. Thus, adding more CH3CN monomers even supports further quasi-linear chain growth.

Dielectric relaxation of water: assessing the impact of localized modes, translational diffusion, and collective dynamics.

A multitude of distinct physical processes and molecular mechanisms have been introduced in the past in an effort to understand the unusual dielectric loss spectrum of water with its pronounced peak at roughly 20 GHz. Our computer simulations including ab initio molecular dynamics provide no evidence for a major impact of cage dynamics or local-diffusive motion on the lineshape below 200 GHz. We also show that the collective motion of hundreds of water molecules and/or their significant diffusive displacements are not required. Instead, the dielectric relaxation of water up to about 200 GHz can be quantitatively described in terms of two unimodal and smoothly decaying spectral contributions.

Aqueous TMAO solution under high hydrostatic pressure.

Trimethylamine N-oxide (TMAO) is a well known osmolyte in nature, which is used by deep sea fish to stabilize proteins against High Hydrostatic Pressure (HHP). We present a combined ab initio molecular dynamics, force field molecular dynamics, and THz absorption study of TMAO in water up to 12 kbar to decipher its solvation properties upon extreme compression. On the hydrophilic oxygen side of TMAO, AIMD simulations at 1 bar and 10 kbar predict a change of the coordination number from a dominating TMAO·(H2O)3 complex at ambient conditions towards an increased population of a TMAO·(H2O)4 complex at HHP conditions. This increase of the TMAO-oxygen coordination number goes in line with a weakening of the local hydrogen bond network, spectroscopic shifts and intensity changes of the corresponding intermolecular THz bands. Using a pressure-dependent HHP force field, FFMD simulations predict a significant increase of hydrophobic hydration from 1 bar up to 4-5 kbar, which levels off at higher pressures up to 10 kbar. THz spectroscopic data reveal two important pressure regimes with spectroscopic inflection points of the dominant intermolecular modes: The first regime (1.5-2 kbar) is barely recognizable in the simulation data. However, it relates well with the observation that the apparent molar volume of solvated TMAO is nearly constant in the biologically relevant pressure range up to 1 kbar as found in the deepest habitats on Earth in the ocean. The second inflection point around 4-5 kbar is related to the amount of hydrophobic hydration as predicted by the FFMD simulations. In particular, the blueshift of the intramolecular CNC bending mode of TMAO at about 390 cm-1 is the spectroscopic signature of increasingly pronounced pressure-induced changes in the solvation shell of TMAO. Thus, the CNC bend can serve as local pressure sensor in the multi-kbar pressure regime.

Probing Local Electrostatics of Glycine in Aqueous Solution by THz Spectroscopy.

Based upon precise terahertz (THz) measurements of the solvated amino acid glycine and accompanying ab-initio molecular-dynamics simulations, we show that the N-C-C-O open/close mode at 315 cm-1 serves as a sensitive, label-free probe for the local protonation of the amide group. Experimentally, we can show that this holds not only for glycine but also for diglycine and valine. The approach is more general, since the changes due to protonation result in intensity changes which can be probed by THz time domain (0-50 cm-1 ) as well as by precise THz-FT spectroscopy (50-400 cm-1 ). A detailed analysis allows us to directly correlate the titration spectra with pKa values. This demonstrates the potential of THz spectroscopy to probe the charge state of a natural amino acid in water in a label-free manner.

Converged quantum simulations of reactive solutes in superfluid helium: The Bochum perspective.

Superfluid helium has not only fascinated scientists for centuries but is also the ideal matrix for the investigation of chemical systems under ultra-cold conditions in helium nanodroplet isolation experiments. Together with related experimental techniques such as helium tagging photodissociation spectroscopy, these methods have provided unique insights into many interesting systems. Complemented by theoretical work, they were additionally able to greatly expand our general understanding of manifestations of superfluid behavior in finite sized clusters and their response to molecular impurities. However, most theoretical studies up to now have not included the reactivity and flexibility of molecular systems embedded in helium. In this perspective, the theoretical foundation of simulating fluxional molecules and reactive complexes in superfluid helium is presented in detail. Special emphasis is put on recent developments for the converged description of both the molecular interactions and the quantum nature of the nuclei at ultra-low temperatures. As a first step, our hybrid path integral molecular dynamics/bosonic path integral Monte Carlo method is reviewed. Subsequently, methods for efficient path integral sampling tailored for this hybrid coupling scheme are discussed while also introducing new developments to enhance the accurate incorporation of the solute⋯solvent coupling. Finally, highly accurate descriptions of the interactions in solute⋯helium systems using machine learning techniques are addressed. Our current automated and adaptive fitting procedures to parameterize high-dimensional neural network potentials for both the full-dimensional potential energy surface of solutes and the solute⋯solvent interaction potentials are concisely presented. They are demonstrated to faithfully represent many-body potential functions able to describe chemically complex and reactive solutes in helium environments seamlessly from one He atom up to bulk helium at the accuracy level of coupled cluster electronic structure calculations. Together, these advances allow for converged quantum simulations of fluxional and reactive solutes in superfluid helium under cryogenic conditions.

Settling the Long-Standing Debate on the Proton Storage Site of the Prototype Light-Driven Proton Pump Bacteriorhodopsin.

Despite decades of research, the location and molecular identity of the proton release group together with the subsequent proton release pathway remain controversial even for the simplest light-driven proton pump, bacteriorhodopsin, according to the most recent experiments and simulations. Yet despite this nagging lack of knowledge for the generic case, even more complex pumps are currently under investigation. The proton release group disclosed by our large-scale simulations satisfies available experimental results, especially the broad Zundel continuum absorption subject to a striking anisotropy observed only recently. Moreover, our simulations delineate the seamless pathway by which the excess proton (being stored in an ultrastrong centered H-bond involving two glutamates) is finally translocated into the extracellular medium.

Acid solvation versus dissociation at "stardust conditions": Reaction sequence matters.

Chemical reactions at ultralow temperatures are of fundamental importance to primordial molecular evolution as it occurs on icy mantles of dust nanoparticles or on ultracold water clusters in dense interstellar clouds. As we show, studying reactions in a stepwise manner in ultracold helium nanodroplets by mass-selective infrared (IR) spectroscopy provides an avenue to mimic these "stardust conditions" in the laboratory. In our joint experimental/theoretical study, in which we successively add H2O molecules to HCl, we disclose a unique IR fingerprint at 1337 cm-1 that heralds hydronium (H3O+) formation and, thus, acid dissociation generating solvated protons. In stark contrast, no reaction is observed when reversing the sequence by allowing HCl to interact with preformed small embryonic ice-like clusters. Our ab initio simulations demonstrate that not only reaction stoichiometry but also the reaction sequence needs to be explicitly considered to rationalize ultracold chemistry.

Toward theoretical terahertz spectroscopy of glassy aqueous solutions: partially frozen solute-solvent couplings of glycine in water.

The molecular-level understanding of THz spectra of aqueous solutions under ambient conditions has been greatly advanced in recent years. Here, we go beyond previous analyses by performing ab initio molecular dynamics simulations of glycine in water with artificially frozen solute or solvent molecules, respectively, while computing the total THz response as well as its decomposition into mode-specific resonances based on the "supermolecular solvation complex" technique. Clamping the water molecules and keeping glycine moving breaks the coupling of glycine to the structural dynamics of the solvent, however, the polarization and dielectric solvation effects in the static solvation cage are still at work since the full electronic structure of the quenched solvent is taken into account. The complementary approach of fixing glycine reveals both the dynamical and electronic response of the solvation cage at the level of its THz response. Moreover, to quantitatively account for the electronic contribution solely due to solvent embedding, the solute species is "vertically desolvated", thus preserving the fully coupled solute-solvent motion in terms of the solute's structural dynamics in solution, while its electronic structure is no longer subject to solute-solvent polarization and charge transfer effects. When referenced to the free simulation of Gly(aq), this three-fold approach allows us to decompose the THz spectral contributions due to the correlated solute-solvent dynamics into entirely structural and purely electronic effects. Beyond providing hitherto unknown insights, the observed systematic changes of THz spectra in terms of peak shifts and lineshape modulations due to conformational freezing and frozen solvation cages might be useful to investigate the solvation of molecules in highly viscous H-bonding solvents such as ionic liquids and even in cryogenic ices as relevant to polar stratospheric and dark interstellar clouds.

Tagging effects on the mid-infrared spectrum of microsolvated protonated methane.

Although bare protonated methane is by now essentially understood at the level of intramolecular large-amplitude motion, scrambling dynamics and broadband vibrational spectra, the microsolvated species still offer plenty of challenges. One aspect is the effect of the attached solvent molecules on the infrared absorption spectra of microsolvated CH5+ complexes compared to the bare parent molecule. In this study we analyze, based on ab initio molecular dynamics simulations, protonated methane molecules that have been microsolvated with up to three hydrogen molecules, i.e. CH5+·(H2) n . In particular, upon introducing a novel multi-channel maximum entropy methodology described herein, we are able to decompose the infrared spectra of these weakly-bound complexes in the frequency window from 1000 to 4500 cm-1 into additive single mode contributions. Detailed comparisons to the bare CH5+ parent reveal that these perturbed modes encode distinct features that depend on the exact microsolvation pattern. Beyond the specific case, such understanding is relevant to assess tagging artifacts in vibrational spectra of parent molecules based on messenger predissociation action spectroscopy.

Aqueous TMAO solutions as seen by theoretical THz spectroscopy: hydrophilic versus hydrophobic water.

Solvation of trimethylamine-N-oxide (TMAO) by water is of great fundamental interest because this small molecule has both strongly hydrophilic and large hydrophobic groups at its opposite ends and, furthermore, stabilizes proteins against temperature and pressure denaturation. Since hydrophilic and hydrophobic groups affect the structural dynamics of the respective solvation water molecules in vastly different ways, we dissect their distinct influences on the THz spectrum of TMAO(aq) by using ab initio molecular dynamics simulations. In particular, we demonstrate that exclusively electronic polarization and charge transfer effects, being absent in the usual fixed-charge biomolecular force fields, are responsible for the significant enhancement of the effective molecular dipole moment of hydrophilic solvation water. This, in turn, leads to pronounced solute-solvent couplings and thus to specific THz modes that involve well-defined H-bond bending and stretching motion being characteristic to hydrophilic solvation. The THz response of individual H-bonded pairs of water molecules involving hydrophobic solvation water, in stark contrast, is nearly indistinguishable from such pairs in bulk water. Transcending the specific case, THz spectroscopy is suggested to be an ideal experimental approach to unravel the controversial piezolytic properties of TMAO including its counteracting effect on pressure-induced denaturation of proteins.

Hydrophilic Solvation Dominates the Terahertz Fingerprint of Amino Acids in Water.

Spectroscopy in the terahertz frequency regime is a sensitive tool to probe solvation-induced effects in aqueous solutions. Yet, a systematic understanding of spectral lineshapes as a result of distinct solvation contributions remains terra incognita. We demonstrate that modularization of amino acids in terms of functional groups allows us to compute their distinct contributions to the total terahertz response. Introducing the molecular cross-correlation analysis method provides unique access to these site-specific contributions. Equivalent groups in different amino acids lead to look-alike spectral contributions, whereas side chains cause characteristic but additive complexities. Specifically, hydrophilic solvation of the zwitterionic groups in valine and glycine leads to similar terahertz responses which are fully decoupled from the side chain. The terahertz response due to H-bonding within the large hydrophobic solvation shell of valine turns out to be nearly indistinguishable from that in bulk water in direct comparison to the changes imposed by the charged functional groups that form strong H-bonds with their hydration shells. Thus, the hydrophilic groups and their solvation shells dominate the terahertz absorption difference, while on the same intensity scale, the influence of hydrophobic water can be neglected.

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.

Constructing accurate interaction potentials to describe the microsolvation of protonated methane by helium atoms.

Protonated methane, CH5+, is not only subject to quasi-rigid vibrational motion which describes its unprotonated parent, CH4, but is dominated by large-amplitude motion even in its quantum ground state. This fluxional behavior leads to hydrogen scrambling which sensitively depends on the underlying flat potential energy surface. Yet, it is largely unknown how fluxional species, such as CH5+, respond to perturbations arising from microsolvation by weakly interacting species, such as those commonly used as tags in messenger-based vibrational action spectroscopies. Here, we construct an intermolecular interaction potential of extrapolated coupled cluster accuracy in order to investigate the microsolvation shell structure of small CH5+·Hen complexes. Having explicitly demonstrated that three-body contributions are essentially negligible, our analytical CH5+He model potential is kept as simple as possible in order to allow for efficient use in the framework of finite-temperature path integral simulations. It is a strictly pairwise additive site-site potential without explicit angular dependence, but critically involves additional pseudo-sites in addition to the usual atom-based interaction sites. The parameterized potential is shown to accurately describe the microsolvation of all low-lying stationary points on the potential energy surface, namely the e-Cs, s-Cs, C2v, and C4v structures. Based on path integral Monte Carlo simulations at ultralow temperature, about 1 K, we disclose that the many-body helium density in three-dimensional space, and thus the microsolvation pattern, depends sensitively on the combination of the solute structure and the number of attached He atoms.

Correlated Particle Motion and THz Spectral Response of Supercritical Water.

Molecular dynamics simulations of supercritical water reveal distinctly different distance-dependent modulations of dipolar response and correlations in particle motion compared to ambient conditions. The strongly perturbed H-bond network of water at supercritical conditions allows for considerable translational and rotational freedom of individual molecules. These changes give rise to substantially different infrared spectra and vibrational density of states at THz frequencies for densities above and below the Widom line that separates percolating liquidlike and clustered gaslike supercritical water.

Water structure and solvation of osmolytes at high hydrostatic pressure: pure water and TMAO solutions at 10 kbar versus 1 bar.

Trimethylamine N-oxide (TMAO) is a protecting osmolyte that stabilizes proteins against both temperature and pressure denaturation. Yet, even the solvation of TMAO itself is not well understood beyond ambient conditions. Here, using ab initio molecular dynamics, we analyze how its solvation structure changes upon compressing its ≈0.5 M aqueous solution from 1 bar to 10 kbar. The neat solvent, liquid water compressed to 10 kbar, is analyzed in detail to provide a meaningful gauge for the pressure-induced solvation changes of the solute. Pure water is shown to prefer to keep four H-bonded water molecules in a locally tetrahedral arrangement up to 10 kbar. The eye-catching shape changes of its oxygen-oxygen radial distribution function, where apparently the entire second peak is shifted into the first one, are traced back to about two more water molecules which are squeezed into the tetrahedral voids that are formed in the first shell by the H-bonded water molecules. These additional molecules increase the coordination number of pure water at 10 kbar significantly, but they are definitely not H-bonded to the central water molecule; rather they are its topological second to fourth H-bonded neighbors. The pressure response of TMAO(aq) is distinctly different, although its radial distribution functions do not change much. Under ambient conditions, the negatively charged oxygen site of the solute, which is strongly hydrophilic, predominantly accepts three H-bonds, whereas a roughly equal population of threefold and square-planar fourfold H-bonding is observed at 10 kbar. Moreover, only a negligible contribution of non-H-bonded water molecules is found in the first-shell region of TMAO even at 10 kbar, in contrast to the pressure response of water itself. In the hydrophobic region of TMAO, the solvating water molecules are found to straddle the three methyl groups at ambient pressure, which remains virtually unchanged upon compressing the solution to 10 kbar. Here, the pressure response is an increase from about 17 to 21 water molecules that solvate the methyl groups despite a sizable radial compression of the hydrophobic solvation shell.

Solvation shell resolved THz spectra of simple aqua ions - distinct distance- and frequency-dependent contributions of solvation shells.

Hydration of ions is a topic of broad relevance in chemistry and biology. Liquid-state terahertz spectroscopy has been demonstrated to be able to detect even small solute-induced changes in the hydrogen bond network dynamics at the solute-water interface. Here, we apply ab initio molecular dynamics simulations to study the solvation of Na(+) and Cl(-) in bulk water in the context of their far-infrared responses. Spatial decomposition schemes for infrared spectra down to the THz regime reveal the importance of both dipolar couplings and correlations in particle motion in these aqueous solutions. The explicit representation of the electronic structure properly captures the solute-solvent polarization effects that are crucial for the interpretation of recent experimental data. This demonstrates that theoretical spectroscopy significantly complements experimental measurements and provides most detailed insights by selectively monitoring the spectral activity due to distinct hydration spheres.