Many remarkable properties of liquid water originate from the ability of its molecules to form hydrogen bonds, each of which emerges as a combination of electrostatic, polarization, dispersion, and donor-acceptor or covalent interactions. In this work, ab initio molecular dynamics was tailored to isolate and switch off the covalent component of interactions between water molecules in simulations. Comparison of simulations with and without covalency shows that a small amount of intermolecular electron density transfer has a profound effect on the structure and dynamics of the hydrogen-bond network and thus on observable properties of room-temperature liquid water.

H4HBEDpa, a new octadentate chelator inspired by the 1960s ligand HBED of Arthur E. Martell, has been investigated for a selection of trivalent metal ions useful in diagnostic and therapeutic applications (Sc3+, Fe3+, Ga3+, In3+, and Lu3+). Complex formation equilibria were thoroughly investigated using combined potentiometric and UV–vis spectrophotometric titrations which revealed effective chelation and high metal-sequestering capacity, in particular for Fe3+, log K FeL = 36.62, [Fe­(HBEDpa)]−. X-ray diffraction study of single crystals revealed that the ligand is preorganized and forms hexa-coordinated complexes with Fe3+ and Ga3+ at acidic pH. Density functional theory (DFT) calculations were applied to probe the geometries and energies of all the possible conformers of [M­(HBEDpa)]− (M = Sc3+, Fe3+, Ga3+, In3+, and Lu3+). DFT calculations confirmed the experimental findings, indicating that [Fe­(HBEDpa)]− is bound tightly in an asymmetric pattern as compared to the symmetrically bound and more open [Ga­(HBEDpa)]−, prone to hydrolysis at higher pH. DFT calculations also showed that a large metal ion such as Lu3+ fully coordinates with HBEDpa4–, forming a binary octadentate complex in its lowest-energy form. Smaller metal ions form six or seven coordinate complexes with HBEDpa4–.

Today, ab initio molecular dynamics (AIMD) relies on the locality of one-electron density matrices to achieve linear growth of computation time with the system size, crucial in large-scale simulations. While Kohn-Sham orbitals strictly localized within predefined radii can offer substantial computational advantages over density matrices, such compact orbitals are not used in AIMD because a compact representation of the electronic ground state is difficult to find. Here, a robust method for maintaining compact orbitals close to the ground state is coupled with a modified Langevin integrator to produce stable nuclear dynamics for molecular and ionic systems. This eliminates a density matrix optimization and enables first orbital-only linear-scaling AIMD. An application to liquid water demonstrates that low computational overhead of the new method makes it ideal for routine medium-scale simulations, while its linear-scaling complexity allows us to extend first-principle studies of molecular systems to completely new physical phenomena on previously inaccessible length scales.

A family of phosphonate-bearing chelators was synthesized to study their potential in metal-based (radio)­pharmaceuticals. Three ligands (H6phospa, H6dipedpa, H6eppy; structures illustrated in manuscript) were fully characterized, including X-ray crystallographic structures of H6phospa and H6dipedpa. NMR spectroscopy techniques were used to confirm the complexation of each ligand with selected trivalent metal ions. These methods were particularly useful in discerning structural information for Sc3+ and La3+ complexes. Solution studies were conducted to evaluate the complex stability of 15 metal complexes. As a general trend, H6phospa was noted to form the most stable complexes, and H6eppy associated with the least stable complexes. Moreover, In3+ complexes were determined to be the most stable, and complexes with La3+ were the least stable, across all metals. Density functional theory (DFT) was employed to calculate structures of H6phospa and H6dipedpa complexes with La3+ and Sc3+. A comparison of experimental 1H NMR spectra with calculated 1H NMR spectra using DFT-optimized structures was used as a method of structure validation. It was noted that theoretical NMR spectra were very sensitive to a number of variables, such as ligand configuration, protonation state, and the number/orientation of explicit water molecules. In general, the inclusion of an explicit second shell of water molecules qualitatively improved the agreement between theoretical and experimental NMR spectra versus a polarizable continuum solvent model alone. Formation constants were also calculated from DFT results using potential-energy optimized structures. Strong dependence of molecular free energies on explicit water molecule number, water molecule configuration, and protonation state was observed, highlighting the need for dynamic data in accurate first-principles calculations of metal–ligand stability constants.

All lithium halides exist in the rock salt crystal structure under ambient conditions. In contrast, common lithium halide classical force fields more often predict wurtzite as the stable structure. This failure of classical models severely limits their range of application in molecular simulations of crystal nucleation and growth. Employing high accuracy density functional theory (DFT) together with classical models, we examine the relative stability of seven candidate crystal structures for lithium halides. We give a detailed examination of the influence of DFT inputs, including the exchange–correlation functional, basis set, and dispersion correction. We show that a high-accuracy basis set, along with an accurate description of dispersion, is necessary to ensure prediction of the correct rock salt structure, with lattice energies in good agreement with the experiment. We also find excellent agreement between the DFT-calculated rock salt lattice parameters and experiment when using the TMTPSS-rVV10 exchange–correlation functional and a large basis set. Detailed analysis shows that dispersion interactions play a key role in the stability of rock salt over closely competing structures. Hartree–Fock calculations, where dispersion interactions are absent, predict the rock salt structure only for LiF, while LiCl, LiBr, and LiI are more stable as wurtzite crystals, consistent with radius ratio rules. Anion–anion second shell dispersion interactions overcome the radius ratio rules to tip the structural balance to rock salt. We show that classical models can be made qualitatively correct in their structural predictions by simply scaling up the pairwise additive dispersion terms, indicating a pathway toward better lithium halide force fields.