Modelling interactions of cationic dimers in He droplets: microsolvation trends in HeK clusters.

We report the results of a detailed theoretical investigation of small K-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.

Structural Stability of the CO @sI Hydrate: a Bottom-Up Quantum Chemistry Approach on the Guest-Cage and Inter-Cage Interactions.

Through reliable first-principles computations, we have demonstrated the impact of CO molecules enclathration on the stability of sI clathrate hydrates. Given the delicate balance between the interaction energy components (van der Waals, hydrogen bonds) present on such systems, we follow a systematic bottom-up approach starting from the individual 5 and 5 6 sI cages, up to all existing combinations of two-adjacent sI crystal cages to evaluate how such clathrate-like models perform on the evaluation of the guest-host and first-neighbors inter-cage effects, respectively. Interaction and binding energies of the CO occupation of the sI cages were computed using DF-MP2 and different DFT/DFT-D electronic structure methodologies.

He Inclusion in Ice-like and Clathrate-like Frameworks: A Benchmark Quantum Chemistry Study of Guest-Host Interactions.

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.

Finite Systems under Pressure: Assessing Volume Definition Models from Parallel-Tempering Monte Carlo Simulations.

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.

Theoretical Study of Cationic Alkali Dimers Interacting with He: Li-He and Na-He van der Waals Complexes.

We present a theoretical study on the potential energy surface and bound states of He-A complexes, where A is one of the alkali Li or Na atoms. The intermolecular interactions were systematically investigated by high-level electronic structure computations, and the corresponding raw data were then employed to reproduce accurate analytical expressions of the potential surfaces. In turn, we used these potentials to evaluate bound configurations of the trimers from nuclear quantum calculations and to extract information on the effect of orientational anisotropy of the forces and the interplay between repulsive and attractive interaction within the potential surfaces.

Quantum chaotic fluctuation-dissipation theorem: Effective Brownian motion in closed quantum systems.

We analytically describe the decay to equilibrium of generic observables of a nonintegrable system after a perturbation in the form of a random matrix. We further obtain an analytic form for the time-averaged fluctuations of an observable in terms of the rate of decay to equilibrium. Our result shows the emergence of a fluctuation-dissipation theorem corresponding to a classical Brownian process, specifically, the Ornstein-Uhlenbeck process.

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

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.

A Systematic Protocol for Benchmarking Guest-Host Interactions by First-Principles Computations: Capturing CO in Clathrate Hydrates.

Clathrate hydrates of CO have been proposed as potential molecular materials in tackling important environmental problems related to greenhouse gases capture and storage. Despite the increasing interest in such hydrates and their technological applications, a molecular-level understanding of their formation and properties is still far from complete. Modeling interactions is a challenging and computationally demanding task, essential to reliably determine molecular properties.

Assessing Intermolecular Interactions in Guest-Free Clathrate Hydrate Systems.

Recently, empty hydrate structures sI, sII, sH, and others have been proposed as low-density ice structures by both experimental observations and computer simulations. Some of them have been synthesized in the laboratory, which motivates further investigations on the stability of such guest-free clathrate structures. Using semiempirical and ab initio-based water models, as well as dispersion-corrected density functional theory approaches, we predict their stability, including cooperative many-body effects, in comparison with reference data from converged wave function-based DF-MP2 electronic structure calculations.

Temperature Dependence of HeBr 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 HeBr van der Waals complex. All rotational states of energies within 7 cm 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 HeBr, respectively, and compared them with those predicted by the rigid rotor model.