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Spatial Contributions to Nuclear Magnetic Shieldings

Jinger, Rahul Kumar; Fliegl, Heike 1; Bast, Radovan; Dimitrova, Maria; Lehtola, Susi; Sundholm, Dage
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)

We develop a methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities which are calculated from the current density via the Biot–Savart relation. Atomic contributions to nuclear magnetic shielding constants can be estimated within our framework with a Becke partitioning scheme. The new features have been implemented in the GIMIC program and are applied in this work to the study of the $^{1}H$ and $^{13}C$ nuclear magnetic shieldings in benzene ($C_{6}H_{6}$) and cyclobutadiene ($C_{4}H_{4}$). The new methodology allows a visual inspection of the spatial origins of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constant of a single nucleus, something which has not been hitherto easily accomplished. Analysis of the shielding densities shows that diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions, as the shielding or deshielding is determined by the direction of the current-density flux with respect to the studied nucleus instead of the tropicity. Becke partitioning of the magnetic shieldings shows that the magnetic shielding contributions mainly originate from the studied atom and its nearest neighbors, confirming the localized character of nuclear magnetic shieldings.

Verlagsausgabe §
DOI: 10.5445/IR/1000135341
Veröffentlicht am 14.07.2021
DOI: 10.1021/acs.jpca.0c10884
Zitationen: 12
Web of Science
Zitationen: 11
Zitationen: 12
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 04.03.2021
Sprache Englisch
Identifikator ISSN: 1089-5639, 1520-5215
KITopen-ID: 1000135341
HGF-Programm 43.31.01 (POF IV, LK 01) Multifunctionality Molecular Design & Material Architecture
Erschienen in The journal of physical chemistry <Washington, DC> / A
Verlag American Chemical Society (ACS)
Band 125
Heft 8
Seiten 1778–1786
Vorab online veröffentlicht am 19.02.2021
Nachgewiesen in Web of Science
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