Ultrahigh-field (73)Ge NMR spectra and DFT calculations of GeO(2) phases reveal distinct parameters for four- and six-coordinate Ge, illustrating the viability of solid-state (73)Ge NMR for structural studies.
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http://dx.doi.org/10.1039/b906642j | DOI Listing |
J Phys Chem Lett
February 2022
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
Metal halide perovskites remain top candidates for higher-performance photovoltaic devices, but concerns about leading lead-based materials remain. Ge perovskites remain understudied for use in solar cells compared to their Sn-based counterparts. In this work, we undertake a combined Ge and Cs solid-state Nuclear Magnetic Resonance (NMR) spectroscopy and density functional theory (DFT) study of the bulk CsGeX (X = Cl, Br, or I) series.
View Article and Find Full Text PDFJ Chem Theory Comput
February 2019
Institute of Nanotechnology , Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1 , 76344 Eggenstein-Leopoldshafen , Germany.
An efficient formulation of scalar-relativistic NMR shielding tensors based on (one-electron) spin-free exact two-component theory (X2C) is presented. It utilizes the diagonal local approximation to the unitary decoupling matrix (DLU), which we recently applied to analytical derivatives [ J. Chem.
View Article and Find Full Text PDFJ Chem Phys
November 2017
Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, UiT The Arctic University of Norway, 9037 Tromsø, Norway.
The NMR chemical shifts and indirect spin-spin coupling constants of 12 molecules containing Si, Ge, Sn, and Pb [X(CCMe), MeX(CCMe), and MeXCCH] are presented. The results are obtained from non-relativistic as well as two- and four-component relativistic density functional theory (DFT) calculations. The scalar and spin-orbit relativistic contributions as well as the total relativistic corrections are determined.
View Article and Find Full Text PDFDalton Trans
October 2017
Dipartimento di Scienze e Tecnologie Biologiche ed Ambientali, Università del Salento, Via Monteroni, I-73100 Lecce, Italy.
In the [ABrI] (A = C, Si, Ge, Sn; n + m = 4) compounds, with the heavier halides bonded to the central IV group elements, the experimental C, Si, Ge and Sn NMR chemical shifts of the central atoms were found to be strictly linearly proportional to the bonded halides ionic radii overall sum ∑(r). Based on this, calibration lines relating the chemical shifts to ∑(r) could be built for the considered subgroup of [ABrI] compounds. Using such calibration lines we could calculate the equivalent NMR radius, r, attributable to each of the bonded hydrogens in [AH] species, according to the overall NMR shielding produced on the central A atom.
View Article and Find Full Text PDFDalton Trans
February 2017
Dipartimento di Scienze e Tecnologie Biologiche ed Ambientali, Università del Salento, Via Monteroni, I-73100 Lecce, Italy.
An inverse linear relationship between Ge, Sn and Pb NMR chemical shifts and the overall sum of ionic radii of coordinated halido ligands has been discovered in tetrahedral [MXY] (M = Ge, Sn, Pb; 1 ≤ n ≤ 4; X, Y = Cl, Br, I) coordination compounds. This finding is consistent with a previously reported correlation found in octahedral, pentacoordinate and square planar platinum complexes. The effect of the coordinated halido ligands acting on the metal as shielding conducting rings is therefore confirmed also by Ge, Sn and Pb NMR spectroscopy.
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