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One of the most fascinating discoveries in recent years, in the cold and low pressure regions of the universe, was the detection of ArH and HeH species. The identification of such noble gas-containing molecules in space is the key to understanding noble gas chemistry. In the present work, we discuss the possibility of [ArH] existence as a potentially detectable molecule in the interstellar medium, providing new data on possible astronomical pathways and energetics of this compound. As a first step, a data-driven approach is proposed to construct a full 3D machine-learning potential energy surface (ML-PES) via the reproducing kernel Hilbert space (RKHS) method. The training and testing data sets are generated from CCSD(T)/CBS[56] computations, while a validation protocol is introduced to ensure the quality of the potential. In turn, the resulting ML-PES is employed to compute vibrational levels and molecular spectroscopic constants for the cation. In this way, the most common isotopologue in ISM, [ArH], was characterized for the first time, while simultaneously, comparisons with previously reported values available for [ArH] are discussed. Our present data could serve as a benchmark for future studies on this system, as well as on higher-order cationic Ar-hydrides of astrophysical interest.

Computational quantum chemistry has become a powerful tool with a wide range of possibilities to solve chemical-physical problems. As a result of this, the interest in the applications of computational quantum chemistry has expanded considerably, and has opened up novel research opportunities. In particular, those related to the characterization of heavy-atoms complexes, as most electronic structure calculations for such systems struggle with the problem posed by the large number of electrons present in them, and consequently, the introduction of relativistic effects. The present study performed an exhaustive assess to characterized the uncommon NgH+ (Ng = Kr, Xe, and Rn) hydride cations in order to provide accurate rovibrational data of their isotopes to assist in the laboratory characterization or even their astronomical detection. Scalar relativistic effects were included, and the ground and first electronically exited states potential curves were obtained from benchmark ab initio CCSD(T)/CBS and MRCI+Q electronic structure calculations. Next, such interaction potentials, correctly extended to long-range asymptotic regions, were employed in quantum bound state calculations and molecular spectroscopic constants were determined for the most abundance 84Kr, 132Xe, and 222Rn isotopes. Our results were discussed in comparison with available experimental and previous theoretical estimates, aiming to treat accuracy issues. The new sets provide reference data that could serve for spectroscopic characterization of such low abundance and high radioactive species.

We report new results on the translational-rotational (T-R) states of the CO2 molecule inside the sI clathrate-hydrate cages. We adopted the multiconfiguration time-dependent Hartree methodology to solve the nuclear molecular Hamiltonian, and to address issues on the T-R couplings. Motivated by experimental X-ray observations on the CO2 orientation in the D and T sI cages, we aim to evaluate the effect of the CO2 -water interaction on quantum dynamics. Thus, we first compared semiempirical and ab initio-based pair interaction model potentials against first-principles DFT-D calculations for ascertaining the importance of nonadditive many-body effects on such guest-host interactions. Our results reveal that the rotational and translational excited states quantum dynamics is remarkably different, with the pattern and density of states clearly affected by the underlying potential model. By analyzing the corresponding the probability density distributions of the calculated T-R eigenstates on both semiempirical and ab initio pair CO2 -water nanocage potentials, we have extracted information on the altered CO2 guest local structure, and we discussed it in connection with experimental data on the orientation of the CO2 molecule in the D and T sI clathrate cages available from neutron diffraction and 13C solid-state NMR studies, as well as in comparison with previous molecular dynamics simulations. Our calculations provide a very sensitive test of the potential quality by predicting the low-lying T-R states and corresponding transitions for the encapsulated CO2 molecule. As such spectroscopic observables have not been measured so far, our results could trigger further detailed experimental and theoretical investigations leading to a quantitative description of the present guest-host interactions.

The structures and energetics of Li 2+ -doped He clusters have been determined by means of evolutionary programming optimizations and classical molecular dynamics simulations. The underlying interactions in the He N Li 2+ complexes are described by sum-of-potentials ab initio-based models. The classical picture of the He atoms surrounding the cationic dimer shows a selective growth of the clusters. By analyzing spatial distribution probabilities, and single-atom evaporative energies from molecular dynamics calculations, we found pronounced drops in the computed energy for N= 2 , 4 and 6, and smaller ones for N= 10 , 13, 15, 18, 20, 22, 24, 27 and 29. The most energetic favored structure (compared to its neighbors) is found when six He atoms are attached in the Li 2+ -cation, forming He 3 -motifs at each side and leading to the formation of the first solvation shell. In turn, as extra He atoms are added, a new shell is started to form at N= 10 , with the He 3 triangles being the building blocks in all classical solid-like structural arrangements in He N Li 2+ clusters. By combining the outcome of our work on the existence of such local solvation microstructures in Li 2+ -doped He clusters together with those from previous studies on alkali ions, we may speculate that such microsolvation effects could influence the short-time solute–solvent dynamics and thus contribute to the observed slow ions’ mobility in He droplets. Graphic Abstract: [Figure not available: see fulltext.].

A water molecule confined inside the C70 fullerene was quantum-mechanically described using a computational approach within the MCTDH framework. Such procedure involves the development of a full-dimensional coupled hamiltonian, with an exact kinetic energy operator, including all rotational, translational and vibrational degrees of freedom of the endofullerene system. In turn, through an effective pairwise potential model, the ground and rotationally excited states of the encapsulated H2 O inside the C70 cage were calculated, and traced back to the isotropic case of the H2 O@C60 endofullerene in order to understand the nature and physical origin of the symmetry breaking observed experimentally in the latter system. Moreover, the computational scheme used here allows to study the quantization of the translational movement of the encapsulated water molecule inside the C70 fullerene, and to investigate the confinement effects in the vibrational energy levels of the H2 O@C70 system.

In the realm of solid water hydrostructures, helium atoms have a tendency to occupy the interstitial spaces formed within the crystal lattice of ice structures. The primary objective of this study is to examine the stability of various ice crystals when influenced by the presence of He atoms. Presenting a first attempt at a detailed computational description of the whole energy components (guest-water, water-water, guest-guest) in the complete crystal unit cells contributes to enhancing the knowledge available about these relatively unexplored helium-water systems, which could potentially benefit future experiments. For this purpose, two different ice structures were considered: the previously established He@ice II system, and the predicted (but currently nonexistent) He@ice XVII system. One of the main features of these He-filled structures is the stability conferred by the weak van der Waals dispersion forces that occur between the host lattice and the guest atoms, in addition to the hydrogen bonds established among the water molecules. Hence, it is crucial to accurately describe these interactions. Therefore, the first part of this research is devoted examining the performance and accuracy of various semi-local and non-local DFT/DFT-D functionals, in comparison with previous experimental and/or high-level computational data. Once the best-performing DFT functional has been identified, the stability of these empty and He-filled structures, including different number of He atoms within the lattices, is analysed in terms of their structural (lattice deformation), mechanical (pressure compression effects) and energetic properties (binding and saturation energies). In this manner, the potential formation of these structures under zero temperature and pressure conditions can be evaluated, while their maximum storage capacity is also determined. The obtained results reveal that, despite the weak underlying interactions, the He encapsulation has a rather notable effect o

The reactive collision between 36 Ar and the 36 ArH+ species has been investigated by means of quantum mechanical (QM), quasiclassical trajectories (QCT) and statistical quantum mechanical (SQM) approaches. Reaction probabilities, cross sections as a function of the energy and rate constants in terms of the temperature have been obtained. Cumulative distributions as a function of the collision time and the inspection of selected QCT corresponding to specific dynamical mechanisms have been analysed. Predictions by means of the SQM method are in good agreement with the QM results, thus supporting the complex-forming nature of the process.

Clathrate hydrates have the ability to encapsulate atoms and molecules within their cavities, and thus they could be potentially large storage capacity materials. The present work studies the multiple cage occupancy effects in the recently discovered He@sII crystal. On the basis of previous theoretical and experimental findings, the stability of He(1/1)@sII, He(1/4)@sII and He(2/4)@sII crystals was analysed in terms of structural, mechanical and energetic properties. For this purpose, first-principles DFT/DFT-D computations were performed by using both semi-local and non-local functionals, not only to elucidate which configuration is the most energetically favoured, but also to scrutinize the relevance of the long-range dispersion interactions in these kinds of compounds. We have encountered that dispersion interactions play a fundamental role in describing the underlying interactions, and different tendencies were observed depending on the choice of the functional. We found that PW86PBE-XDM shows the best performance, while the non-local functionals tested here were not able to correctly account for them. The present results reveal that the most stable configuration is the one presenting singly occupied D cages and tetrahedrally occupied H cages (He(1/4)@sII) in line with the experimental observation.

We performed first-principles computations to investigate the complex interplay of molecular interaction energies in determining the lattice structure and stability of CO2@sH clathrate hydrates. Density functional theory computations using periodic boundary conditions were employed to characterize energetics and the key structural properties of the sH clathrate crystal under pressure, such as equilibrium lattice volume and bulk modulus. The performance of exchange−correlation functionals together with recently developed dispersion-corrected schemes was evaluated in describing interactions in both short-range and long-range regions of the potential. Structural relaxations of the fully CO2-filled and empty sH unit cells yield crystal structure and lattice energies, while their compressibility parameters were derived by including the pressure dependencies. The present quantum chemistry computations suggest anisotropy in the compressibility of the sH clathrate hydrates, with the crystal being less compressible along the a-axis direction than along the c-axis one, in distinction from nearly isotropic sI and sII structures. The detailed results presented here give insight into the complex nature of the underlying guest−host interactions, checking earlier assumptions, providing critical tests, and improving estimates. Such entries may eventually lead to better predictions of thermodynamic properties and formation conditions, with a direct impact on emerging hydrate-based technologies.

Dissolved ions in aqueous media are ubiquitous in many physicochemical processes, with a direct impact on research fields, such as chemistry, climate, biology, and industry. Ions play a crucial role in the structure of the surrounding network of water molecules as they can either weaken or strengthen it. Gaining a thorough understanding of the underlying forces from small clusters to bulk solutions is still challenging, which motivates further investigations. Through a systematic analysis of the interaction energies obtained from high-level electronic structure methodologies, we assessed various dispersion-corrected density functional approaches, as well as ab initio-based data-driven potential models for halide ion-water clusters. We introduced an active learning scheme to automate the generation of optimally weighted datasets, required for the development of efficient bottom-up anion-water models. Using an evolutionary programming procedure, we determined optimized and reference configurations for such polarizable and first-principles-based representation of the potentials, and we analyzed their structural characteristics and energetics in comparison with estimates from DF-MP2 and DFT+D quantum chemistry computations. Moreover, we presented new benchmark datasets, considering both equilibrium and non-equilibrium configurations of higher-order species with an increasing number of water molecules up to 54 for each F, Cl, Br, and I anions, and we proposed a validation protocol to cross-check methods and approaches. In this way, we aim to improve the predictive ability of future molecular computer simulations for determining the ongoing conflicting distribution of different ions in aqueous environments, as well as the transition from nanoscale clusters to macroscopic condensed phases.

We report the results of a detailed and accurate investigation focused on structures and energetics of poly-hydrated halides employing first-principles polarizable halide-water potentials to describe the underlying forces. Following a bottom-up data-driven potential approach, we initially looked into the classical behavior of higher-order X(HO) clusters. We have located several low-lying energies, such as global and local minima, structures for each cluster, with various water molecules (up to N = 8) surrounding the halide anion (X = F, Cl, Br, I), employing an evolutionary programming method. It is found that the F-water clusters exhibit different structural configurations than the heavier halides, however independently of the halide anion, all clusters show in general a selective growth with the anion preferring to be connected to the outer shell of the water molecule arrangements. In turn, path-integral molecular dynamics simulations are performed to incorporate explicitly nuclear quantum and thermal effects in describing the nature of halide ion microsolvation in such prototypical model systems. Our data reveal that at low finite temperatures, nuclear quantum effects affect certain structural properties, such as weakening hydrogen bonding between the halide anion and water molecules, with minor distortions in the water network beyond the first hydration shell, indicating local structure rearrangements. Such structural characteristics and the promising cluster size trends observed in the single-ion solvation energies motivated us to draw connections of small size cluster data to the limits of continuum bulk values, toward the investigation of the challenging computational modeling of bulk single ion hydration.

We explore the origin of the anomalous splitting of the 1 levels reported experimentally for the HO@C endofullerene, in order to give some insight about the physical interpretations of the symmetry breaking observed. We performed fully-coupled quantum computations within the multiconfiguration time-dependent Hartree approach employing a rigorous procedure to handle such computationally challenging problems. We introduce two competing physical models, and discuss the observed unconventional quantum patterns in terms of anisotropy in the interfullerene interactions, caused by the change in the off-center position of the encapsulated water molecules inside the cage or the uniaxial C-cage distortion, arising from noncovalent bonding upon water's encapsulation, or exohedral fullerene perturbations. Our results show that both scenarios could reproduce the experimentally observed rotational degeneracy pattern, although quantitative agreement with the available experimental rotational levels splitting value has been achieved by the model that considers an uniaxial elongation of the C-cage. Such finding supports that the observed symmetry breaking could be mainly caused by the distortion of the fullerene cage. However, as nuclear quantum treatments rely on the underlying interactions, a decisive conclusion hinges on the availability of their improved description, taken into account both endofullerene and exohedral environments, from forthcoming highly demanding electronic structure many-body interaction studies.

The dynamics of the formation of a specific clathrate hydrate as well as its thermodynamic transitions depend on the interactions between the trapped molecules and the host water lattice. The molecular-level understanding of the different underlying processes benefits not only the description of the properties of the system, but also allows the development of multiple technological applications such as gas storage, gas separation, energy transport, etc. In this work we investigate the stability of periodic crystalline structures, such as He@sI and He@sII clathrate hydrates by first-principles computations. We consider such host water networks interacting with a guest He atom using selected density functional theory approaches, in order to explore the effects on the encapsulation of a light atom in the sI/sII crystals, by deriving all energy components (guest-water, water-water, guest-guest). Structural properties and energies were first computed by structural relaxations of the He-filled and empty sI/sII unit cells, yielding lattice and compressibility parameters comparable to experimental and theoretical values available for those hydrates. According to the results obtained, the He enclathration in the sI/sII unit cells is a stabilizing process, and both He@sI and He@sII clathrates, considering single cage occupancy, are predicted to be stable whatever the XDM or D4 dispersion correction applied. Our results further reveal that despite the weak underlying interactions the He encapsulation has a rather notable effect on both lattice parameters and energetics, with the He@sII being the most energetically favorable in accord with recent experimental observations.

Dissolved ions in aqueous media are ubiquitous in many physicochemical processes, with a direct impact on research fields, such as chemistry, climate, biology, and industry. Ions play a crucial role in the structure of the surrounding network of water molecules as they can either weaken or strengthen it. Gaining a thorough understanding of the underlying forces from small clusters to bulk solutions is still challenging, which motivates further investigations. Through a systematic analysis of the interaction energies obtained from high-level electronic structure methodologies, we assessed various dispersion-corrected density functional approaches, as well as ab initio-based data-driven potential models for halide ion-water clusters. We introduced an active learning scheme to automate the generation of optimally weighted datasets, required for the development of efficient bottom-up anion-water models. Using an evolutionary programming procedure, we determined optimized and reference configurations for such polarizable and first-principles-based representation of the potentials, and we analyzed their structural characteristics and energetics in comparison with estimates from DF-MP2 and DFT+D quantum chemistry computations. Moreover, we presented new benchmark datasets, considering both equilibrium and non-equilibrium configurations of higher-order species with an increasing number of water molecules up to 54 for each F, Cl, Br, and I anions, and we proposed a validation protocol to cross-check methods and approaches. In this way, we aim to improve the predictive ability of future molecular computer simulations for determining the ongoing conflicting distribution of different ions in aqueous environments, as well as the transition from nanoscale clusters to macroscopic condensed phases.

We introduce an efficient quantum fully coupled computational scheme within the multiconfiguration time-dependent Hartree (MCTDH) approach to handle the otherwise extremely costly computations of translational-rotational-vibrational states and energies of light-molecule endofullenes. Quantum calculations on energy levels are reported for a water molecule inside Cfullerene by means of such a systematic approach that includes all nine degrees of freedom of HO@Cand does not consider restrictions above them. The potential energy operator is represented as a sum of natural potentials employing then-mode expansion, along with the exact kinetic energy operator, by introducing a set of Radau internal coordinates for the HO molecule. On the basis of the present rigorous computations, various aspects of the quantized intermolecular dynamics upon confinement of HO@Care discussed, such as the rotational energy level splitting and the significant frequency shifts of the encapsulated water molecule vibrations. The impact of water encapsulation on quantum features is explored, and insights into the nature of the underlying forces are provided, highlighting the importance of a reliable first-principles description of the guest-host interactions.

Theoretical–computational studies together with recent astronomical observations have shown that under extreme conditions in the interstellar medium (ISM), complexes of noble gases may be formed. Such observations have generated a wide range of possibilities. In order to identify new species containing such atoms, the present study gathers spectroscopic data for noble gas hydride cations, NgH+ (Ng = He, Ne, Ar) from high-level ab initio quantum chemistry computations, aiming to contribute in understanding the chemical bonding and electron sharing in these systems. The interaction potentials are obtained from CCSD(T)/CBS and MRCI+Q calculations using large basis sets, and then employed to compute vibrational levels and molecular spectroscopic constants for all known stable isotopologues of ground state NgH+ cations. Comparisons with previously reported values available are discussed, indicating that the present data could serve as a benchmark for future studies on these systems and on higher-order cationic noble gas hydrides of astrophysical interest.

We performed first-principles computations to investigate guest-host/host-host effects on the encapsulation of the CO2 molecule in sII clathrate hydrates from finite-size clusters up to periodic 3D crystal lattice systems. Structural and energetic properties were first computed for the individual and first-neighbors clathrate-like sII cages, where highly accurate ab initio quantum chemical methods are available nowadays, allowing in this way the assessment of the density functional (DFT) theoretical approaches employed. The performance of exchange-correlation functionals together with recently developed dispersion-corrected schemes was evaluated in describing interactions in both short-range and long-range regions of the potential. On this basis, structural relaxations of the CO2-filled and empty sII unit cells yield lattice and compressibility parameters comparable to experimental and previous theoretical values available for sII hydrates. According to these data, the CO2 enclathration in the sII clathrate cages is a stabilizing process, either by considering both guest-host and host-host interactions in the complete unit cell or only the guest-water energies for the individual clathrate-like sII cages. CO2@sII clathrates are predicted to be stable whatever the dispersion correction applied and in the case of single cage occupancy are found to be more stable than the CO2@sI structures. Our results reveal that DFT approaches could provide a good reasonable description of the underlying interactions, enabling the investigation of formation and transformation processes as a function of temperature and pressure.

We implemented a systematic procedure for treating the quantal rotations by including all translational and vibrational degrees of freedom for any triatomic bent molecule in any embedded or confined environment, within the MCTDH framework. Fully coupled quantum treatments were employed to investigate unconventional properties in nanoconfined molecular systems. In this way, we facilitate a complete theoretical analysis of the underlying dynamics that enables us to compute the energy levels and the nuclear spin isomers of a single water molecule trapped in a C fullerene cage. The key point lies in the full 9D description of both nuclear and electronic degrees of freedom, as well as a reliable representation of the guest-host interaction. The presence of occluded impurities or inhomogeneities due to noncovalent interactions in the interfullerene environment could modify aspects of the potential, causing significant coupling between otherwise uncoupled modes. Using specific n-mode model potentials, we obtained splitting patterns that confirm the effects of symmetry breaking observed by experiments in the ground ortho-HO state. Further, our investigation reveals that the first rotationally excited states of the encapsulated ortho- and para-HO have also raised their 3-fold degeneracy. In view of the complexity of the problem, our results highlight the importance of accurate and computational demanding approaches for building up predictive models for such nanoconfined molecules.

The formation of specific clathrate hydrates and their trans-formation at given thermodynamic conditions depends on theinteractions between the guest molecule/s and the host waterlattice. Understanding their structural stability is essential tocontrol structure-property relations involved in different tech-nological applications. Thus, the energetic aspects relative toCO2@sI clathrate hydrate are investigated through the compu-tation of the underlying interactions, dominated by hydrogenbonds and van der Waals forces, from first-principles electronicstructure approaches. The stability of the CO2@sI clathrate isevaluated by combining bottom-up and top-down approaches.Guest-free and CO2guest-filled aperiodic cages, up to thegradually CO2occupation of the entire sI periodic unit cellswere considered. Saturation, cohesive and binding energies forthe systems are determined by employing a variety of densityfunctionals and their performance is assessed. The dispersioncorrections on the non-covalent interactions are found to beimportant in the stabilization of the CO2@sI energies, with theencapsulation of the CO2into guest-free/empty cage/latticebeing always an energetically favorable process for most of thefunctionals studied. The PW86PBE functional with XDM orD3(BJ) dispersion corrections predicts a lattice constant inaccord to the experimental values available, and simultaneouslyprovides a reliable description for the guest-host interactions inthe periodic CO2@sI crystal, as well as the energetics of itsprogressive single cage occupancy process. It has been foundthat the preferential orientation of the single CO2in the large sIcrystal cages has a stabilizing effect on the hydrate, concludingthat the CO2@sI structure is favored either by considering theindividual building block cages or the complete sI unit cellcrystal. Such benchmark and methodology cross-check studiesbenefit new data-driven model research by providing high-quality training information, with new insights

Doped He droplets constitute an important environment as ultracold homogeneous matrices for spectroscopic studies. Alkali metal dopants have a series of interesting properties due to their unusual bonding behavior. Neutral atoms attached to the surface of the droplet, forming eventually cold molecules via collisions, while charged dopants form solvation shells, related with the low mobility of the ions in experiments. So, investigations on the underlying intermolecular, markedly orientational ionic, forces, and on the miscoscopic structures of alkali-cation-He complexes is essential.

Through reliable first-principles computations, we have demon-strated the impact of CO2molecules enclathration on thestability of sI clathrate hydrates. Given the delicate balancebetween the interaction energy components (van der Waals,hydrogen bonds) present on such systems, we follow a system-atic bottom-up approach starting from the individual 512and51262sI cages, up to all existing combinations of two-adjacent sIcrystal cages to evaluate how such clathrate-like modelsperform on the evaluation of the guest-host and first-neighborsinter-cage effects, respectively. Interaction and binding energiesof the CO2occupation of the sI cages were computed using DF-MP2 and different DFT/DFT D electronic structure method-ologies. The performance of selected DFT functionals, togetherwith various semi-classical dispersion corrections schemes, werevalidated by comparison with reference ab initio DF-MP2 data,as well as experimental data from x-ray and neutron diffractionstudies available. Our investigation confirms that the inclusionof the CO2in the cage/s is an energetically favorable process,with the CO2molecule preferring to occupy the large 51262sIcages compared to the 512ones. Further, the present resultsconclude on the rigidity of the water cages arrangements,showing the importance of the inter-cage couplings in thecluster models under study. In particular, the guest-cageinteraction is the key factor for the preferential orientation ofthe captured CO2molecules in the sI cages, while the inter-cageinteractions seems to cause minor distortions with the CO2guest neighbors interactions do not extending beyond thelarge 51262sI cages. Such findings on these clathrate-like modelsystems are in accord with experimental observations, drawinga direct relevance to the structural stability of CO2@sI clathrates.

We report the results of a detailed theoretical investigation of small K2 +-doped He clusters. The structural characteristics and stabilities of such cations are determined from ab initio electronic structure calculations at the MRCI+Q level of theory. The underlying interactions show a multireference character and such effects are analyzed. The interaction potentials are constructed employing an interpolation technique within the inverse problem theory method, while the nuclear quantum effects are computed for the trimers, their spatial arrangements are discussed, and information was extracted on the orientational anisotropy of the forces. We found that energetically the most stable conformer corresponds to linear arrangements that are taking place under large amplitude vibrations, with high zero-point energy. We have further looked into the behavior of higher-order species with various He atoms surrounding the cationic dopant. By using a sum of potentials approach and an evolutionary programming method, we analyzed the structural stability of clusters with up to six He atoms in comparison with interactions energies obtained from MRCI+Q quantum chemistry computations. Structures containing Hen motifs that characterize pure rare gas clusters, appear for the larger K2 +-doped He clusters, showing selective growth during the microsolvation process of the alkali-dimer cation surrounded by He atoms. Such results indicate the existence of local solvation microstructures in these aggregates, where the cationic impurity could get trapped for a short time, contributing to the slow ionic mobility observed experimentally in ultra-cold He-droplets

Energetics and structural properties of selected type and size He@hydrate frameworks, e.g., from regular structured ice channels to clathrate-like cages, are presented from first-principles quantum chemistry methods. The scarcity of information on He@hydrates makes such complexes challenging targets, while their computational study entails an interesting and arduous task. Some of them have been synthesized in the laboratory, which motivates further investigations on their stability. Hence, the main focus is to examine the performance and accuracy of different wave function-based electronic structure methods, such as MP2, CCSD(T), their explicitly correlated (F12) and domain-based local pair-natural orbital (DLPNO) analogs, as well as modern and conventional density functional theory (DFT) approaches, and analytical model potentials available. Different structures are considered, starting from the "simplest system"formed by a noble gas atom (such as He) and one water molecule, followed by the study of the "fundamental units"present in all ice-like and clathrate-like frameworks (such as pentamers and hexamers) and finally the description of interactions in the "building blocks"of three-dimensional (3D) ice channels (e.g., horizontal and perpendicular ice II and Ih) and clathrate-like cages, such as the 512 present in the most common sI, sII, and sH clathrate-hydrate structures. The idea is to provide well-converged DLPNO-CCSD(T) and DFMP2/CBS reference datasets that in turn are used to validate how DFT functionals (in total, 29 approaches from generalized-gradient approximation (GGA), meta-GGA, to hybrid and range-separated functionals, including dispersion correction treatments, were checked) and analytical semiempirical/ab initio-based potentials perform compared with high-level alternatives. Within all tested approaches, those best-performing were identified and classified. Most of the DFT/DFT-D functionals, as well as available analytical pairwise model potentials

We have investigated different approaches to handling parallel-tempering Monte Carlo (PTMC) simulations in the isothermal-isobaric ensemble of molecular cluster/nanoparticle systems for predicting structural phase diagram transitions. We have implemented various methodologies that consist of treating pressure implicitly through its effect on the volume. Thus, the main problem in the simulations under nonzero pressure becomes the volume definition of the finite nonperiodic system, and we considered approaches based on the particles' coordinates. Various volume models, namely container-volume, particle-volume, average-volume, ellipsoids-volume, and convex hull-volume, were employed, and the required corrections for each of them in the Monte Carlo computations were introduced. Finally, we explored the effects of volume/pressure changes for all models on structural phase transitions of a test system, such as the small "icelike" (HO) water cluster. The temperature and pressure dependence of the cluster's heat capacity and energy-volume Pearson correlation coefficient were studied, phase diagrams were constructed using a multiple-histogram method, and attempts were made to identify phase transitions to particular cluster structures. Our results show significant differences between the employed volume models, and we discuss all pressure-induced, such as solid-solid-, solid-liquid-, and liquid-gas-like, phase transformations in the present study.

Ion specific effects in aqueous environments are of fundamental interest across interdisciplinary fields, with modeling of ion-pair/ion-water/ water-water interactions being one of the main research topics. So far, the water-water interactions have been widely studied yielding a variety of water potential models of increasing complexity. Although extensive experimental and theoretical studies have been reported, questions on how ions change the water network and the properties of their aqueous solutions are still open, demanding an accurate description of the underlying intermolecular forces. In this work, the first principle approaches are employed to develop generalized representations for such interactions coupled to available and reliable water models for studying ion-hydrates from finite-size clusters to bulk solutions.