Coordination of Mercury(II) in Water Promoted over Hydrolysis in Solvated Clusters [Hg(H2O)1-6](aq)2+: Insights from Relativistic Effects and Free Energy Analysis.

Understanding the nature of the interaction between mercury(II) ions, Hg2+, and water molecules is crucial to describe the stability and chemical behavior of structures formed during solvation, as well as the conditions that favor the Hg2+ coordination or inducing water hydrolysis. In our study, we explored exhaustively the potential energy surface of Hg2+ with up to six water molecules. We analyzed electronic and Gibbs free energies, binding, and nuclear magnetic resonance parameters. We used the zeroth-order regular approximation Hamiltonian, including scalar and spin-orbit relativistic corrections for free energy calculations and geometry optimizations to explore the interplay between electron correlation and relativistic effects. We analyzed intermolecular interactions with energy decomposition analysis, quantum theory of atoms in molecules, and natural bond orbital. Additionally, we used the four-component Dirac Hamiltonian to compute solvent effect on the magnetic shielding and J-coupling constants. Our results revealed that the water hydrolysis by Hg2+ requires a minimum of three water molecules. We found that the interaction between Hg2+ and water molecules is an orbital interaction due to relativistic effects and the most stable structures are opened-shape clusters, reducing the number of oxygen-mercury contacts and maximizing the formation of hydrogen bonds among water molecules. In these types of clusters, Hg2+ promotes the water hydrolysis over coordination with oxygen atoms. However, when we considered the change associated with the transfer of a cluster from the ideal gas to a solvated system, our solvation free energy analysis revealed that closed-shape clusters are more favorable, maximizing the number of oxygen-mercury contacts and reducing the formation of hydrogen bonds among water molecules. This finding suggests that, under room conditions, the coordination of Hg2+ is more favorable than hydrolysis. Our results have significant implications for understanding Hg2+ behavior in water, helping to develop targeted strategies for mercury remediation and management, and contributing to advancements in the broader field of environmental chemistry.

Relativistic quantum calculations to understand the contribution of f-type atomic orbitals and chemical bonding of actinides with organic ligands.

The nuclear waste problem is one of the main interests of rare earth and actinide element chemistry. Studies of actinide-containing compounds are at the frontier of the applications of current theoretical methods due to the need to consider relativistic effects and approximations to the Dirac equation in them. Here, we employ four-component relativistic quantum calculations and scalar approximations to understand the contribution of f-type atomic orbitals in the chemical bonding of actinides (Ac) to organic ligands. We studied the relativistic quantum structure of an isostructural family made of Plutonium (Pu), Americium (Am), Californium (Cf), and Berkelium (Bk) atoms with the redox-active model ligand DOPO (2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate). Crystallographic structures were available to validate our calculations for all mentioned elements except for Cf. In short, state-of-the-art relativistic calculations were performed at different levels of theory to investigate the influence of relativistic and electron correlation effects on geometrical structures and bonding energies of Ac-DOPO3 complexes (Ac = Pu, Am, Cf, and Bk): (1) the scalar (sc) and spin-orbit (so) relativistic zeroth order regular approximation (ZORA) within the hybrid density functional theory (DFT) and (2) the four-component Dirac equation with both the Dirac-Hartree-Fock (4c-DHF) and Lévy-Leblond (LL) Hamiltonians. We show that sr- and so-ZORA-DFT could be used as efficient theoretical models to first approximate the geometry and electronic properties of actinides which are difficult to synthesize or characterize, but knowing that the higher levels of theory, like the 4c-DHF, give closer results to experiments. We also performed spin-free 4c calculations of geometric parameters for the Americium and Berkelium compounds. To the best of our knowledge, this is the first time that these kinds of large actinide compounds (the largest contains 67 atoms and 421 electrons) have been studied with highly accurate four-component methods (all-electron calculations with 6131 basis functions for the largest compound). We show that relativistic effects play a key role in the contribution of f-type atomic orbitals to the frontier orbitals of Ac-DOPO3 complexes. The analysis of the results obtained applying different theoretical schemes to calculate bonding energies is also given.

The LRESC-Loc Model to Analyze Magnetic Shieldings with Localized Molecular Orbitals.

The leading electronic mechanisms of relativistic effects in the NMR magnetic shieldings of heavy-atom (HA) containing molecules are well described by the linear response with elimination of small components model (LRESC). We show here first results from a new version of the LRESC model written in terms of localized molecular orbitals (LMOs) which is coined as LRESC-Loc. Those LMOs resemble "chemist's orbitals", representing lone-pairs, atomic cores, and bonds. The whole set of relativistic effects are expressed in terms of non-ligand-dependent and ligand-dependent contributions. We show the electronic origin of trends and behavior of different mechanisms in molecular systems which contain heavy elements that belong to any of the IB to VIIA groups of the periodic table. The SO mechanism has a well-defined dependence with the LPs (LPσ and LPπ) when the HAs have them, but the non-SO mechanisms mostly depend on other LMOs. In addition we propose here that the SO mechanism can be used to characterize interactions involving LPs and the non-SO mechanisms to characterize covalent and close-shell interactions. All our main results are in accord with previous findings, though we are now able to analyze them in a different manner.

Understanding the nature of bonding interactions in the carbonic acid dimers.

Carbonic acid dimer, (CA)2, (H2CO3)2, helps to explain the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H-O, H-O⋯H-O, C=O⋯C=O, C=O⋯O-H, and C-O⋯O-H. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer. We dissect the nature of intermolecular interactions and assess their influence on stability. For a set of 40 (H2CO3)2 isomers, C=O⋯H-O hydrogen bonds between the carbonyl oxygen in one CA molecule and the acidic hydrogen in the hydroxyl group at a second CA molecule are the major stabilizing factors because they exhibit the shortest interaction distances, the largest orbital interaction energies, and the largest accumulation of electron densities around the corresponding bond critical points. In most cases, these are closed-shell hydrogen bonds, however, in a few instances, some covalent character is induced. Bifurcated hydrogen bonds are a common occurrence in the dimers of carbonic acid, resulting in a complex picture with multiple orbital interactions of various strengths. Two anti-anti monomers interacting via the strongest C=O⋯H-O hydrogen bonds are the ingredients for the formation of the lowest energy dimers. Graphical Abstract Carbonic acid dimer, (CA)2, (H2CO3)2, helps explaining the existence of this acid as a stable species, different to a simple sum between carbon dioxide and water. Five distinct, well-characterized types of intermolecular interactions contribute to the stabilization of the dimers, namely, C=O⋯H-O, H-O⋯O-H, C=O⋯C=O, C=O⋯O-C, and C-O⋯O-C. In many cases, the stabilizing hydrogen bonds are of at least the same strength as in the water dimer.

Grid-based algorithm to search critical points, in the electron density, accelerated by graphics processing units.

Using a grid-based method to search the critical points in electron density, we show how to accelerate such a method with graphics processing units (GPUs). When the GPU implementation is contrasted with that used on central processing units (CPUs), we found a large difference between the time elapsed by both implementations: the smallest time is observed when GPUs are used. We tested two GPUs, one related with video games and other used for high-performance computing (HPC). By the side of the CPUs, two processors were tested, one used in common personal computers and other used for HPC, both of last generation. Although our parallel algorithm scales quite well on CPUs, the same implementation on GPUs runs around 10× faster than 16 CPUs, with any of the tested GPUs and CPUs. We have found what one GPU dedicated for video games can be used without any problem for our application, delivering a remarkable performance, in fact; this GPU competes against one HPC GPU, in particular when single-precision is used.