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

Literature Information

Publication Date 2020-12-09
DOI 10.1039/D0CP06012G
Impact Factor 3.676
Authors

Laura Abella, Adam Philips, Jochen Autschbach


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Abstract

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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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