Direct magnetic-field dependence of NMR chemical shift

Literature Information

Publication Date 2020-04-06
DOI 10.1039/D0CP01372B
Impact Factor 3.676
Authors

Anu M. Kantola, Perttu Lantto, Ivo Heinmaa, Juha Vaara, Jukka Jokisaari


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Abstract

Nuclear shielding and chemical shift are considered independent of the magnetic-field strength. Ramsey proposed on theoretical grounds in 1970 that this may not be valid for heavy nuclei. Here we present experimental evidence for the direct field dependence of shielding, using 59Co shielding in Co(acac)3 [tris(acetylacetonate)cobalt(III)] as an example. We carry out NMR experiments in four field strengths for this low-spin diamagnetic Co(III) complex, which features a very large and negative nuclear shielding constant of the central Co nucleus. This is due to a magnetically accessible, low-energy eg ← t2g orbital excitation of the d6 system. The experiments result in temperature-dependent magnetic-field dependence of −5.7 to −5.2 ppb T−2 of the 59Co shielding constant, arising from the direct modification of the electron cloud of the complex by the field. First-principles multiconfigurational non-linear response theory calculations verify the sign and order of magnitude of the experimental results.

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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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