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.

The accuracy limit of chemical shift predictions for species in aqueous solution.

Interpreting NMR experiments benefits from first-principles predictions of chemical shifts. Reaching the accuracy limit of theory is relevant for unambiguous structural analysis and dissecting theoretical approximations. Since accurate chemical shift measurements are based on using internal reference compounds such as trimethylsilylpropanesulfonate (DSS), a detailed comparison of experimental with theoretical data requires simultaneous consideration of both target and reference species ensembles in the same solvent environment. Here we show that ab initio molecular dynamics simulations to generate liquid-state ensembles of target and reference compounds, including explicitly their short-range solvation environments and combined with quantum-mechanical solvation models, allows for predicting highly accurate 1H (∼0.1-0.5 ppm) and aliphatic 13C (∼1.5 ppm) chemical shifts for aqueous solutions of the model compounds trimethylamine N-oxide (TMAO) and N-methylacetamide (NMA), referenced to DSS without any system-specific adjustments. This encompasses the two peptide bond conformations of NMA identified by NMR. The results are used to derive a general-purpose guideline set for predictive NMR chemical shift calculations of NMA in the liquid state and to identify artifacts of force field models. Accurate predictions are only obtained if a sufficient number of explicit water molecules is included in the quantum-mechanical calculations, disproving a purely electrostatic model of the solvent effect on chemical shifts.

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.

Quantum Nuclear Delocalization and its Rovibrational Fingerprints.

Quantum mechanics dictates that nuclei must undergo some delocalization. In this work, emergence of quantum nuclear delocalization and its rovibrational fingerprints are discussed for the case of the van der Waals complex HHe 3 + ${{\rm{HHe}}_3^ + }$ . The equilibrium structure of HHe 3 + ${{\rm{HHe}}_3^ + }$ is planar and T-shaped, one He atom solvating the quasi-linear He-H+ -He core. The dynamical structure of HHe 3 + ${{\rm{HHe}}_3^ + }$ , in all of its bound states, is fundamentally different. As revealed by spatial distribution functions and nuclear densities, during the vibrations of the molecule the solvating He is not restricted to be in the plane defined by the instantaneously bent HHe 2 + ${{\rm{HHe}}_2^ + }$ chomophore, but freely orbits the central proton, forming a three-dimensional torus around the HHe 2 + ${{\rm{HHe}}_2^ + }$ chromophore. This quantum delocalization is observed for all vibrational states, the type of vibrational excitation being reflected in the topology of the nodal surfaces in the nuclear densities, showing, for example, that intramolecular bending involves excitation along the circumference of the torus.

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.

Dissecting the Molecular Origin of g-Tensor Heterogeneity and Strain in Nitroxide Radicals in Water: Electron Paramagnetic Resonance Experiment versus Theory.

Nitroxides are common EPR sensors of microenvironmental properties such as polarity, numbers of H-bonds, pH, and so forth. Their solvation in an aqueous environment is facilitated by their high propensity to form H-bonds with the surrounding water molecules. Their g- and A-tensor elements are key parameters to extracting the properties of their microenvironment. In particular, the gxx value of nitroxides is rich in information. It is known to be characterized by discrete values representing nitroxide populations previously assigned to have different H-bonds with the surrounding waters. Additionally, there is a large g-strain, that is, a broadening of g-values associated with it, which is generally correlated with environmental and structural micro-heterogeneities. The g-strain is responsible for the frequency dependence of the apparent line width of the EPR spectra, which becomes evident at high field/frequency. Here, we address the molecular origin of the gxx heterogeneity and of the g-strain of a nitroxide moiety (HMI: 2,2,3,4,5,5-hexamethylimidazolidin-1-oxyl, C9H19N2O) in water. To treat the solvation effect on the g-strain, we combined a multi-frequency experimental approach with ab initio molecular dynamics simulations for structural sampling and quantum chemical EPR property calculations at the highest realistically affordable level, including an explicitly micro-solvated HMI ensemble and the embedded cluster reference interaction site model. We could clearly identify the distinct populations of the H-bonded nitroxides responsible for the gxx heterogeneity experimentally observed, and we dissected the role of the solvation shell, H-bond formation, and structural deformation of the nitroxide in the creation of the g-strain associated with each nitroxide subensemble. Two contributions to the g-strain were identified in this study. The first contribution depends on the number of hydrogen bonds formed between the nitroxide and the solvent because this has a large and well-understood effect on the gxx-shift. This contribution can only be resolved at high resonance frequencies, where it leads to distinct peaks in the gxx region. The second contribution arises from configurational fluctuations of the nitroxide that necessarily lead to g-shift heterogeneity. These contributions cannot be resolved experimentally as distinct resonances but add to the line broadening. They can be quantitatively analyzed by studying the apparent line width as a function of microwave frequency. Interestingly, both theory and experiment confirm that this contribution is independent of the number of H-bonds. Perhaps even more surprisingly, the theoretical analysis suggests that the configurational fluctuation broadening is not induced by the solvent but is inherently present even in the gas phase. Moreover, the calculations predict that this broadening decreases upon solvation of the nitroxide.

Structural Sampling and Solvation Models for the Simulation of Electronic Spectra: Pyrazine as a Case Study.

The impact of sampling methods on spectral broadening in the gas phase and on the convergence of spectra in aqueous solution when using microsolvation, continuum solvation, and hybrid models is studied using pyrazine as a test case. For the sake of comparing classical Maxwell-Boltzmann and Wigner samplings in the gas phase, static and time-resolved X-ray absorption spectra after photoexcitation to the lowest 1B2u(ππ*) state, as well as the static UV-vis absorption spectrum, are considered. In addition, the UV-vis absorption spectrum of pyrazine in aqueous solution is also computed in order to systematically investigate its convergence with the number of explicitly included solvent shells with and without taking bulk solvation effects into account with the conductor-like screening model to represent implicit water beyond such explicit solute complexes. Concerning the static and time-resolved X-ray absorption spectra of pyrazine at the carbon K-edge as well as its UV-vis absorption spectrum in the gas phase, we find that these spectra obtained with Wigner and Maxwell-Boltzmann samplings substantially agree. For the UV-vis absorption spectrum in the aqueous solution, only the first two energetically low-lying bands converge quickly with the size of the explicitly included solvation shells, either with or without an additional continuum solvation taken into account. In stark contrast, calculations of the higher-lying excitations relying on finite microsolvated clusters without additional continuum solvation severely suffer from unphysical charge-transfer excitations into Rydberg-like orbitals at the cluster/vacuum interface. This finding indicates that computational UV-vis absorption spectra covering sufficiently high-lying states converge only if continuum solvation of the explicitly microsolvated solutes is included in the models.

Onset of Rotational Decoupling for a Molecular Ion Solvated in Helium: From Tags to Rings and Shells.

Little is known about how rotating molecular ions interact with multiple ^{4}He atoms and how this relates to microscopic superfluidity. Here, we use infrared spectroscopy to investigate ^{4}He_{N}⋯H_{3}O^{+} complexes and find that H_{3}O^{+} undergoes dramatic changes in rotational behavior as ^{4}He atoms are added. We present evidence of clear rotational decoupling of the ion core from the surrounding helium for N>3, with sudden changes in rotational constants at N=6 and 12. In sharp contrast to studies on small neutral molecules microsolvated in helium, accompanying path integral simulations show that an incipient superfluid effect is not needed to account for these findings.

Deciphering the Impact of Helium Tagging on Flexible Molecules: Probing Microsolvation Effects of Protonated Acetylene by Quantum Configurational Entropy.

Helium, the lightest and most weakly interacting noble gas, is well-known for its unsurpassed chemical inertness. In many applications of helium in experimental techniques, such as tagging, messenger, or nanodroplet isolation action spectroscopy of molecules or complexes, it is assumed that the interaction of helium with the respective species, and thus the resulting interaction-induced perturbation, is small enough not to affect their structure and dynamics. Here, we probe the impact of one up to many attached helium atoms on protonated acetylene─an important nonclassical carbocation subject to three-center two-electron bonding in its ground state structure─using highly accurate interaction potentials in conjunction with entropy-based higher-order nonlinear correlation analysis. In particular, using neural network potentials at CCSD(T) accuracy, we disclose the specific structural perturbations due to the tagging of C2H3+ with up to 20 He atoms at a temperature of 1 K. Analysis reveals that microsolvation by helium influences the structure of C2H3+ noticeably, while our investigation of the quantum configurational information entropy additionally shows that correlations between individual orientational degrees of freedom are affected as a function of cluster size. In particular, it is found that the most probable bridge-like structure of the ro-vibrational quantum ground state of C2H3+, which is nonplanar and trans-bent in contrast to the perfectly planar equilibrium structure, becomes increasingly more localized upon adding helium atoms. The remarkably nonlinear behavior of the angular correlations as a function of cluster size is traced back to the buildup of the quantum microsolvation shell that enhances anisotropy up to NHe = 6 while more and more isotropic solvation takes over beyond six. Our approach is general and thus sets the stage to investigate the salient effects on the structure of flexible molecules due to tagging beyond the specific case.

Deciphering the Properties of Nanoconfined Aqueous Solutions by Vibrational Sum Frequency Generation Spectroscopy.

When confined between walls at nanometer distances, water exhibits surprisingly different properties with reference to bare interfacial water. Based on computer simulations, we demonstrate how vibrational sum frequency generation (VSFG) spectroscopy can be used-even with very mild symmetry breaking-to discriminate multilayer water in wide slit pores from both bilayer and monolayer water confined within molecularly narrow pores. Applying the technique, the VSFG lineshapes of monolayer, bilayer, and multilayer water are found to differ in characteristic ways, which is explained by their distinct density stratifications giving rise to different H-bonding patterns in the respective solvation layers.

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.

State-resolved infrared spectrum of the protonated water dimer: revisiting the characteristic proton transfer doublet peak.

The infrared (IR) spectra of protonated water clusters encode precise information on the dynamics and structure of the hydrated proton. However, the strong anharmonic coupling and quantum effects of these elusive species remain puzzling up to the present day. Here, we report unequivocal evidence that the interplay between the proton transfer and the water wagging motions in the protonated water dimer (Zundel ion) giving rise to the characteristic doublet peak is both more complex and more sensitive to subtle energetic changes than previously thought. In particular, hitherto overlooked low-intensity satellite peaks in the experimental spectrum are now unveiled and mechanistically assigned. Our findings rely on the comparison of IR spectra obtained using two highly accurate potential energy surfaces in conjunction with highly accurate state-resolved quantum simulations. We demonstrate that these high-accuracy simulations are important for providing definite assignments of the complex IR signals of fluxional molecules.

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.

Infrared Spectra at Coupled Cluster Accuracy from Neural Network Representations.

Infrared spectroscopy is key to elucidating molecular structures, monitoring reactions, and observing conformational changes, while providing information on both structural and dynamical properties. This makes the accurate prediction of infrared spectra based on first-principle theories a highly desirable pursuit. Molecular dynamics simulations have proven to be a particularly powerful approach for this task, albeit requiring the computation of energies, forces and dipole moments for a large number of molecular configurations as a function of time. This explains why highly accurate first-principles methods, such as coupled cluster theory, have so far been inapplicable for the prediction of fully anharmonic vibrational spectra of large systems at finite temperatures. Here, we push cutting-edge machine learning techniques forward by using neural network representations of energies, forces, and in particular dipoles to predict such infrared spectra fully at "gold standard" coupled cluster accuracy as demonstrated for protonated water clusters as large as the protonated water hexamer, in its extended Zundel configuration. Furthermore, we show that this methodology can be used beyond the scope of the data considered during the development of the neural network models, allowing for the computation of finite-temperature infrared spectra of large systems inaccessible to explicit coupled cluster calculations. This substantially expands the hitherto existing limits of accuracy, speed, and system size for theoretical spectroscopy and opens up a multitude of avenues for the prediction of vibrational spectra and the understanding of complex intra- and intermolecular couplings.

Neural network interaction potentials for para-hydrogen with flexible molecules.

The study of molecular impurities in para-hydrogen (pH2) clusters is key to push forward our understanding of intra- and intermolecular interactions, including their impact on the superfluid response of this bosonic quantum solvent. This includes tagging with only one or very few pH2, the microsolvation regime for intermediate particle numbers, and matrix isolation with many solvent molecules. However, the fundamental coupling between the bosonic pH2 environment and the (ro-)vibrational motion of molecular impurities remains poorly understood. Quantum simulations can, in principle, provide the necessary atomistic insight, but they require very accurate descriptions of the involved interactions. Here, we present a data-driven approach for the generation of impurity⋯pH2 interaction potentials based on machine learning techniques, which retain the full flexibility of the dopant species. We employ the well-established adiabatic hindered rotor (AHR) averaging technique to include the impact of the nuclear spin statistics on the symmetry-allowed rotational quantum numbers of pH2. Embedding this averaging procedure within the high-dimensional neural network potential (NNP) framework enables the generation of highly accurate AHR-averaged NNPs at coupled cluster accuracy, namely, explicitly correlated coupled cluster single, double, and scaled perturbative triples, CCSD(T*)-F12a/aVTZcp, in an automated manner. We apply this methodology to the water and protonated water molecules as representative cases for quasi-rigid and highly flexible molecules, respectively, and obtain AHR-averaged NNPs that reliably describe the corresponding H2O⋯pH2 and H3O+⋯pH2 interactions. Using path integral simulations, we show for the hydronium cation, H3O+, that umbrella-like tunneling inversion has a strong impact on the first and second pH2 microsolvation shells. The automated and data-driven nature of our protocol opens the door to the study of bosonic pH2 quantum solvation for a wide range of embedded impurities.

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.

Zwitter Ionization of Glycine at Outer Space Conditions due to Microhydration by Six Water Molecules.

We investigate glycine microsolvation with water molecules, mimicking astrophysical conditions, in our laboratory by embedding these clusters in helium nanodroplets at 0.37 K. We recorded mass selective infrared spectra in the frequency range 1500-1800 cm^{-1} where two bands centered at 1630 and 1724 cm^{-1} were observed. By comparison with the extensive accompanying calculations, the band at 1630 cm^{-1} was assigned to the COO^{-} asymmetric stretching mode of the zwitter ion and the band at 1724 cm^{-1} was assigned to redshifted C=O stretch within neutral clusters. We show that zwitter ion formation of amino acids readily occurs with only few water molecules available even under extreme conditions.

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.

A Joint Venture of Ab Initio Molecular Dynamics, Coupled Cluster Electronic Structure Methods, and Liquid-State Theory to Compute Accurate Isotropic Hyperfine Constants of Nitroxide Probes in Water.

The isotropic hyperfine coupling constant (HFCC, Aiso) of a pH-sensitive spin probe in a solution, HMI (2,2,3,4,5,5-hexamethylimidazolidin-1-oxyl, C9H19N2O) in water, is computed using an ensemble of state-of-the-art computational techniques and is gauged against X-band continuous wave electron paramagnetic resonance (EPR) measurement spectra at room temperature. Fundamentally, the investigation aims to delineate the cutting edge of current first-principles-based calculations of EPR parameters in aqueous solutions based on using rigorous statistical mechanics combined with correlated electronic structure techniques. In particular, the impact of solvation is described by exploiting fully atomistic, RISM integral equation, and implicit solvation approaches as offered by ab initio molecular dynamics (AIMD) of the periodic bulk solution (using the spin-polarized revPBE0-D3 hybrid functional), embedded cluster reference interaction site model integral equation theory (EC-RISM), and polarizable continuum embedding (using CPCM) of microsolvated complexes, respectively. HFCCs are obtained from efficient coupled cluster calculations (using open-shell DLPNO-CCSD theory) as well as from hybrid density functional theory (using revPBE0-D3). Re-solvation of "vertically desolvated" spin probe configuration snapshots by EC-RISM embedding is shown to provide significantly improved results compared to CPCM since only the former captures the inherent structural heterogeneity of the solvent close to the spin probe. The average values of the Aiso parameter obtained based on configurational statistics using explicit water within AIMD and from EC-RISM solvation are found to be satisfactorily close. Using either such explicit or RISM solvation in conjunction with DLPNO-CCSD calculations of the HFCCs provides an average Aiso parameter for HMI in aqueous solution at 300 K and 1 bar that is in good agreement with the experimentally determined one. The developed computational strategy is general in the sense that it can be readily applied to other spin probes of similar molecular complexity, to aqueous solutions beyond ambient conditions, as well as to other solvents in the longer run.