Electronic g values of Na+–NO and Cu+–NO complexes in zeolites: Analysis using a relativistic density functional method

Literature Information

Publication Date 2003-04-23
DOI 10.1039/B300737E
Impact Factor 3.676
Authors

Konstantin M. Neyman, Dmitri I. Ganyushin, Vladimir A. Nasluzov, Notker Rösch, Andreas Pöppl, Martin Hartmann


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Abstract

Electronic g values of molecular systems are usually difficult to interpret. We propose a new tool for the analysis of g values in terms of contributions of particular atomic orbitals. This tool benefits from a direct relationship between ground-state relativistic Kohn–Sham orbitals and g values in our novel scheme which takes spin–orbit effects into account self-consistently and employs two-component orbital wave functions obtained after a Douglas–Kroll decoupling of the four-component Dirac–Kohn–Sham equation to calculate electronic g values. We rationalize the notable difference in the g tensor anisotropy of adsorption complexes of an NO probe with charge compensating Na+ and Cu+ cations in zeolites. g components of the Na+–NO species, all three of them measured and calculated smaller than the free-electron value ge, reflect the essentially electrostatic adsorption mechanism. At variance, two g components larger than ge are obtained for the complex Cu+–NO and they are shown to manifest covalent interactions due to Cu 3d orbitals.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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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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