Probing the Electrode-Electrolyte Interface of Sodium/Glyme-Based Battery Electrolytes.

Sodium-ion batteries (NIBs) are promising systems for large-scale energy storage solutions; yet, further enhancements are required for their commercial viability. Improving the electrochemical performance of NIBs goes beyond the chemical description of the electrolyte and electrode materials as it requires a comprehensive understanding of the underlying mechanisms that govern the interface between electrodes and electrolytes. In particular, the decomposition reactions occurring at these interfaces lead to the formation of surface films. Previous work has revealed that the solvation structure of cations in the electrolyte has a significant influence on the formation and properties of these surface films. Here, an experimentally validated molecular dynamics study is performed on a 1 M NaTFSI salt in glymes of different lengths placed between two graphite electrodes having a constant bias potential. The focus of this study is on describing the solvation environment around the sodium ions at the electrode-electrolyte interface as a function of glyme chain length and applied potential. The results of the study show that the diglyme/TFSI system presents features at the interface that significantly differ from those of the triglyme/TFSI and tetraglyme/TFSI systems. These computational predictions are successfully corroborated by the experimentally measured capacitance of these systems. In addition, the dominant solvation structures at the interface explain the electrochemical stability of the system as they are consistent with cyclic voltammetry characterization.

Computational Energy Spectra of the H2 O@C70 Endofullerene.

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.

Unraveling the Origin of Symmetry Breaking in H2 O@C60 Endofullerene Through Quantum Computations.

We explore the origin of the anomalous splitting of the 101 levels reported experimentally for the H2 O@C60 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 C60 -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 C60 -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.

Encapsulation of a Water Molecule inside C60 Fullerene: The Impact of Confinement on Quantum Features.

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 C60 fullerene by means of such a systematic approach that includes all nine degrees of freedom of H2O@C60 and does not consider restrictions above them. The potential energy operator is represented as a sum of natural potentials employing the n-mode expansion, along with the exact kinetic energy operator, by introducing a set of Radau internal coordinates for the H2O molecule. On the basis of the present rigorous computations, various aspects of the quantized intermolecular dynamics upon confinement of H2O@C60 are 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.

Fully Coupled Quantum Treatment of Nanoconfined Systems: A Water Molecule inside a Fullerene C60.

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 C60 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-H2O state. Further, our investigation reveals that the first rotationally excited states of the encapsulated ortho- and para-H2O 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.

Temperature Dependence of HeBr2 Isomers' Stability through Rovibrational Multiconfiguration Time-Dependent Hartree Calculations.

The multiconfiguration time-dependent Hartree (MCTDH) method using a six-dimensional Hamiltonian that includes all rotational and vibrational degrees of freedom and an ab initio potential energy surface was employed to calculate the rovibronic states of the HeBr2 van der Waals complex. All rotational states of energies within 7 cm -1 with respect to the energy of the linear ground state were calculated without restriction of the total angular momentum. In total, we obtained 500 and 320 rotationally excited states of the ground vibrational T-shaped and linear isomers of the HeBr2, respectively, and compared them with those predicted by the rigid rotor model. A thermodynamic model was then introduced to determine the relative stability of the two conformers as a function of the temperature. On the basis of the present results, the linear conformers were found to be energetically more stable than the T-shaped ones by 1.14 cm-1 at T = 0 K, whereas conversion from linear to T-shaped complexes was observed at temperatures above 2.87 K.