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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.

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 on both lattice parameters and energetics, and therefore, the guest-host interactions are far from being negligible. Besides, both ice crystals are predicted to remain stable when filled with He atoms, with ice XVII exhibiting a higher capacity for accommodating a larger number of guest atoms within its interstitial spaces.

One of the several possibilities offered by the interesting clathrate hydrates is the opportunity to encapsulate several atoms or molecules, in such a way that more efficient storage materials could be explored or new molecules that otherwise do not exist could be created. These types of applications are receiving growing attention from technologists and chemists, given the future positive implications that they entail. In this context, we investigated the multiple cage occupancy of helium clathrate hydrates, to establish stable novel hydrate structures or ones similar to those predicted previously by experimental and theoretical studies. To this purpose, we analyzed the feasibility of including an increased number of He atoms inside the small (D) and large (H) cages of the sII structure through first-principles properly assessed density functional approaches. On the one hand, we have computed energetic and structural properties, in which we examined the guest-host and guest-guest interactions in both individual and two-adjacent clathrate-like sII cages by means of binding and evaporation energies. On the other hand, we have carried out a thermodynamical analysis on the stability of such He-containing hydrostructures in terms of changes in enthalpy, Δ H , Gibbs free energy, Δ G , and entropy, Δ S , during their formation process at various temperature and pressure values. In this way, we have been able to make a comparison with experiments, reaffirming the ability of computational DFT approaches to describe such weak guest-host interactions. In principle, the most stable structure involves the encapsulation of one and four He atoms inside the D and H sII cages, respectively; however, more He atoms could be entrapped under lower temperature and/or higher pressure thermodynamic conditions. We foresee such accurate computational quantum chemistry approaches contributing to the current emerging machine-learning model development.

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.

We have assessed the performance and accuracy of different wavefunction-based electronic structure methods, such as DFMP2 and domain-based local pair-natural orbital (DLPNO-CCSD(T)), as well as a variety of density functional theory (DFT) approaches on He@(H 2 O) N cage systems. We have selected representative clathrate-like structures corresponding to the building blocks present in each of the sI, sII and sH natural gas clathrate hydrates, and we have carefully studied the interaction between a He atom with each of their individual cages. We reported well-converged DFMP2 and DLPNO-CCSD(T) reference data, together with interaction and cohesive energies of four different density functionals (two GGA, revPBE and PW86PBE, and two hybrids, B3LYP and PBE0), including diverse dispersion correction schemes (D3(0), D3(BJ), D4 and XDM) for both He-filled and empty clathrate-like cages. After the analysis of the results, we came to the conclusion that the PW86PBE functional, with both XDM and D4 corrections, and the PBE0-D4 functional present reasonably adequate approaches to describe the guest-host noncovalent interactions that take place in such He clathrate hydrates. Taking into account that the He@sII is the only helium clathrate that scientists have been able to synthesize recently, we have performed a thermodynamic study on the individual 5 12 and 5 12 6 4 cages present in the sII crystal. We determined the change in enthalpy, Δ H , and in Gibbs free energy, Δ G , at various temperatures and pressures, and we found out that in the range of experimental conditions the reactions associated with the encapsulation of the He atom inside the cages are exothermic and spontaneous. Finally, we highlighted the importance of an accurate description of the interaction in He@water mixtures, as a crucial component in construction of reliable data-driven models.

We performed first-principles computations to investigate guest-host/host-host effects on the encapsulation of the CO 2 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 CO 2 -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 CO 2 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. CO 2 @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 CO 2 @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.

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 I h ) and clathrate-like cages, such as the 5 12 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, face difficulties in describing both hydrogen-bonded water frameworks and dispersion bound He-water interactions. Including dispersion corrections yields an overall well-balanced performance for LCωPBE-D3BJ and PBE0-D4 functionals. Such benchmark datasets can benefit research into the development of new cheminformatics models, as can serve to guide and cross-check methodologies, lending increased predicted power to future molecular simulations for investigating the role of structures and phase transitions from nanoscale clusters to macroscopic crystalline structures.