Ab initio molecular dynamics study of sodium NMR chemical shifts in the methylamine solution of [Na+ [2.2.2]cryptand Na-].

The sodium anion (Na-) was once thought to behave like a 'genuine' anion, with both the [Ne] core and the 3s valence shell interacting very weakly with their environments. In the present work, following a recent study of the surprisingly small quadrupolar line widths of Na-, NMR shielding calculations were carried out for the Na-/Na+ [2.2.2]cryptand system solvated in methylamine, based on ab initio molecular dynamics simulations, followed by detailed analyses of the shielding constants. The results confirm that Na- does not act like a quasi-free ion that interacts only weakly with its surroundings. Rather, the filled 3s shell of Na- interacts strongly with its chemical environment, but only weakly with the ion's own core and the nucleus, and it isolates the core from the chemical environment. As a consequence, the Na- ion appears in NMR experiments like a free ion.

Proton NMR relaxation from molecular dynamics: intramolecular and intermolecular contributions in water and acetonitrile.

NMR relaxation rates for protons in liquid water and neat acetonitrile were computed based on ab initio molecular dynamics (aiMD) with forces from Kohn-Sham (KS) theory as well as force-field (FF) based classical dynamics. Intra- and intermolecular dipole-dipole contributions were separated, and nearly quantitative agreement with experiment was obtained for water. Spin-rotation (SR) contributions to the intramolecular relaxation rate in acetonitrile were computed using nuclear SR coupling tensors obtained from KS theory. Their inclusion improved the total computed intramolecular rate to within a factor of two of experiment. Insufficient sampling of rare short-time collision events between neighboring acetonitrile molecules in the simulations is hypothesized as a major source of error in the intermolecular contributions.

Structure and bonding in rhodium coordination compounds: a 103Rh solid-state NMR and relativistic DFT study.

This study demonstrates the application of 103Rh solid-state NMR (SSNMR) spectroscopy to inorganic and organometallic coordination compounds, in combination with relativistic density functional theory (DFT) calculations of 103Rh chemical shift tensors and their analysis with natural bond orbital (NBO) and natural localized molecular orbital (NLMO) protocols, to develop correlations between 103Rh chemical shift tensors, molecular structure, and Rh-ligand bonding. 103Rh is one of the least receptive NMR nuclides, and consequently, there are very few reports in the literature. We introduce robust 103Rh SSNMR protocols for stationary samples, which use the broadband adiabatic inversion-cross polarization (BRAIN-CP) pulse sequence and wideband uniform-rate smooth-truncation (WURST) pulses for excitation, refocusing, and polarization transfer, and demonstrate the acquisition of 103Rh SSNMR spectra of unprecedented signal-to-noise and uniformity. The 103Rh chemical shift tensors determined from these spectra are complemented by NBO/NLMO analyses of contributions of individual orbitals to the 103Rh magnetic shielding tensors to understand their relationship to structure and bonding. Finally, we discuss the potential for these experimental and theoretical protocols for investigating a wide range of materials containing the platinum group elements.

Unified Description of Proton NMR Relaxation in Water, Acetonitrile, and Methane from Molecular Dynamics Simulations in the Liquid, Supercritical, and Gas Phases.

A comprehensive calculation of proton NMR relaxation in water, acetonitrile, and methane across a wide range of the phase diagram is provided via ab initio and force-field-based molecular dynamics simulations. The formalism used for the spin-rotation (SR) contribution to relaxation is developed for use with any molecular symmetry and utilizes the full molecular SR tensors, which are calculated from first-principles via Kohn-Sham (KS) DFT. In combination with calculations of the dipolar contribution, near-quantitative agreement with total measured relaxation rates is achieved.

Quadrupolar NMR Relaxation of Aqueous 127I-, 131Xe, and 133Cs+: A First-Principles Approach from Dynamics to Properties.

Quadrupolar NMR relaxation rates were computed for aqueous 133Cs+, 131Xe, and 127I- via Kohn-Sham (KS) density functional theory-based ab initio molecular dynamics and KS calculations of the electric field gradient (EFG) tensors along the trajectories. The resulting rates are within a factor of 1-3 of the experimental values and can be compared to available results from classical dynamics and EFGs from electrostatic models with corrections via Sternheimer antishielding factors. Relativistic effects are shown to have an enhancing effect on the magnitude of the EFGs. An analysis of the EFGs was carried out in terms of localized molecular orbitals to elucidate contributions from the solvent versus solute polarization and assess the validity of the Sternheimer approximation for these systems.

The Sodium Anion Is Strongly Perturbed in the Condensed Phase Even Though It Appears Like a Free Ion in Nuclear Magnetic Resonance Experiments.

Solvated sodium anions (Na-) were thought to behave essentially like isolated gas-phase ions that interact only weakly with their environments. For example, 23Na NMR signals for solvated Na- are very sharp, despite the potential for strong quadrupolar broadening. The sharp NMR signals appear to indicate a nearly spherical electron density of the ion. For the present study, ab initio molecular dynamics simulations and quadrupolar relaxation rate calculations were carried out for the Na-/Na+ [2.2.2]cryptand system solvated in methylamine, followed by detailed analyses of the electric field gradient at the sodium nuclei. It is found that Na- does not behave like a quasi-free ion interacting only weakly with its environment. Rather, the filled 3s shell of Na- interacts weakly with the ion's own core and the nucleus, causing Na- to appear in NMR experiments like a free ion.

Quadrupolar 14N NMR Relaxation from Force-Field and Ab Initio Molecular Dynamics in Different Solvents.

Quadrupolar NMR spin relaxation rates and corresponding line widths were computed for the quadrupolar nucleus 14N for neat acetonitrile as well as for 1-methyl-1,3-imidazole and 1-methyl-1,3,4-triazole in different solvents. Molecular dynamics (MD) was performed with forces from the Kohn-Sham (KS) theory (ab initio MD) and force-field molecular mechanics (classical MD), followed by KS electric field gradient (EFG) calculations. For acetonitrile the agreement of the 14N line width with experiment is very good. Relative line widths for the azole nitrogens are improved over simpler approximations used previously in conjunction with single-point calculations at the multiconfigurational self-consistent field level. Overall, the NMR line widths are computed within a factor of 2 of the experimental values, giving access to reasonable estimates both of the dynamic EFG variance in the solvated systems as well as the associated correlation times that determine the relaxation rates.

Quadrupolar NMR Relaxation from ab Initio Molecular Dynamics: Improved Sampling and Cluster Models versus Periodic Calculations.

Quadrupolar NMR relaxation rates are computed for 17O and 2H nuclei of liquid water, and of 23Na+, and 35Cl- in aqueous solution via Kohn-Sham (KS) density functional theory ab initio molecular dynamics (aiMD) and subsequent KS electric field gradient (EFG) calculations along the trajectories. The calculated relaxation rates are within about a factor of 2 of experimental results and improved over previous aiMD simulations. The relaxation rates are assessed with regard to the lengths of the simulations as well as configurational sampling. The latter is found to be the more limiting factor in obtaining good statistical sampling and is improved by averaging over many equivalent nuclei of a system or over several independent trajectories. Further, full periodic plane-wave basis calculations of the EFGs are compared with molecular-cluster atomic-orbital basis calculations. The two methods deliver comparable results with nonhybrid functionals. With the molecular-cluster approach, a larger variety of electronic structure methods is available. For chloride, the EFG computations benefit from using a hybrid KS functional.