This article presents results of first-principles calculations of quadrupolar parameters measured by solid-state nuclear magnetic measurement (NMR) spectroscopy. Different computational methods based on density functional theory were used to calculate the quadrupolar parameters. Through a series of illustrations from different areas of solid state inorganic chemistry, it is shown how quadrupolar solid-state NMR properties can be tackled by a theoretical approach and can yield structural information.
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http://dx.doi.org/10.1002/jcc.21028 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is typically explained in terms of quadrupole-quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
In the theory of condensed-phase spectroscopy, local field effect is of general importance to account for intermolecular electrostatic interactions. The present paper extends the microscopic treatment of local field effects on the sum frequency generation (SFG) spectroscopy to incorporate quadrupole interactions, since their roles have been increasingly recognized in the SFG spectroscopy. The extended theory involves some corrections to the conventional formulas of the nonlinear susceptibilities in both the interface and bulk regions, including the χIQB term.
View Article and Find Full Text PDFJ Colloid Interface Sci
April 2025
School of Physics and Astronomy, The University of Edinburgh, Peter Guthrie Tait Road, Edinburgh EH9 3FD, UK; Department of Physics, University of Gothenburg, SE-41296 Gothenburg, Sweden; University of Münster, Institute of Physical Chemistry, Corrensstr. 28/30, 48149 Münster, Germany. Electronic address:
Hypothesis: Ellipsoidal particles confined at liquid interfaces exhibit complex self-assembly due to quadrupolar capillary interactions, favouring either tip-to-tip or side-to-side configurations. However, predicting and controlling which structure forms remains challenging. We hypothesize that introducing a polymer-based soft shell around the particles will modulate these capillary interactions, providing a means to tune the preferred self-assembly configuration based on particle geometry and shell properties.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Univ Rennes, ENSCR, CNRS, ISCR-UMR6226, Université de Rennes, Rennes 35042, France.
Metal halide perovskites, including some of their related perovskitoid structures, form a semiconductor class of their own, which is arousing ever-growing interest from the scientific community. With halides being involved in the various structural arrangements, namely, pure corner-sharing MX (M is metal and X is halide) octahedra, for perovskite networks, or alternatively a combination of corner-, edge-, and/or face-sharing for related perovskitoids, they represent the ideal probe for characterizing the way octahedra are linked together. Well known for their inherently large quadrupolar constants, which is detrimental to the resolution of nuclear magnetic resonance spectroscopy, most abundant halide isotopes (Cl, Br, I) are in turn attractive for magnetic field-free nuclear quadrupolar resonance (NQR) spectroscopy.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States.
In this work, a machine learning mapping approach for predicting the properties of atomistic systems is reported. Within this approach, the atomic orbital overlap, density, or Kohn-Sham (KS) Fock matrix elements obtained at a low level of theory such as extended tight-binding have been used as input features to predict the electric field gradient (EFG) tensors at a higher level of theory such as those obtained with hybrid functionals. It is shown that the machine-learning-predicted EFG tensors can be used to compute spin relaxation rates of several ions in aqueous solutions.
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