Solid-state NMR of quadrupolar halogen nuclei

Chapman, Rebecca P.; Widdifield, Cory M.; Bryce, David L.

doi:10.1016/j.pnmrs.2009.05.001

Cited by 70 publications

(85 citation statements)

References 156 publications

(218 reference statements)

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“…The 35/37 Cl SSNMR spectra were referenced to 0.1 mol/dm 3 NaCl in D 2 O at 0 ppm 47 using solid KCl as a secondary reference (d iso (KCl(s)) = 8.54 ppm). 32 Calcium-43 SSNMR spectra were referenced to a 2 mol/dm 3 aqueous solution of CaCl 2 (d iso = 0 ppm). 48 Chlorine and calcium pulse widths were established using the 35/37 Cl and 43 Ca SSNMR signals of solid KCl and saturated CaCl 2 (aq), respectively.…”

Section: Solid-state 35/37 CL and 43 Ca Nmrmentioning

confidence: 99%

“…12,14,29,[31][32][33][34][35][36][37] We have observed that the NMR spectra of these nuclei are very sensitive to the EFG produced by the ions and molecules of the surrounding environment. There exist two NMR-active chlorine nuclides ( 35 Cl and 37 Cl), both of which are quadrupolar (I( 35/37 Cl) = 3/2) and of moderately high abundance (75.779(46)% for 35 Cl, 24.221(46)% for 37 Cl).…”

Section: Introductionmentioning

confidence: 99%

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A multinuclear solid-state magnetic resonance and GIPAW DFT study of anhydrous calcium chloride and its hydrates

Widdifield

Bryce

2011

Can. J. Chem.

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The group 2 metal halides and corresponding metal halide hydrates serve as useful model systems for understanding the relationship between the electric field gradient (EFG) and chemical shift (CS) tensors at the halogen nuclei and the local molecular and electronic structure. Here, we present a 35/37 Cl and 43 Ca solid-state nuclear magnetic resonance (SSNMR) study of CaCl2. The 35 Cl nuclear quadrupole coupling constant, 8.82(8) MHz, and the isotropic chlorine CS, 105(8) ppm (with respect to dilute NaCl(aq)), are different from the values reported previously for this compound, as well as those reported for CaCl2·2H2O. Chlorine-35 SSNMR spectra are also presented for CaCl2·6H2O, and when taken in concert, the SSNMR observations for CaCl2, CaCl2·2H2O, and CaCl2·6H2O clearly demonstrate the sensitivity of the chlorine EFG and CS tensors to the local symmetry and to changes in the hydration state. For example, the value of diso decreases with increasing hydration. Gauge-including projector-augmented wave (GIPAW) density functional theory (DFT) calculations are used to substantiate the experimental SSNMR findings, to rule out the presence of other hydrates in our samples, to refine the hydrogen positions in CaCl2·2H2O, and to explore the isostructural relationship between CaCl2 and CaBr2. Finally, the 43 Ca CS tensor span is measured to be 31 (5) ppm for anhydrous CaCl2, which represents only the fifth CS tensor span measurement for calcium. Résumé : Les halogénures des métaux du groupe 2 et les hydrates d'halogénures métalliques sont des systèmes modèles qui permettent comprendre la relation entre le gradient du champ électrique (GCE) et les tenseurs du déplacement chimique (DC) au niveau du noyau d'halogène et la structure électronique et moléculaire locale. Dans ce travail, on présente les résul-tats d'une étude de résonance magnétique nucléaire à l'état solide (RMN-ES) du 35/37 Cl et 43 Ca du CaCl 2 . Les valeurs de la constante de couplage quadripolaire nucléaire du 35 Cl, 8,82(8) MHz, et le DC isotrope du chlore, 105(8) ppm [par rapport au NaCl(aq) dilué], sont différentes de celles rapportées pour ce composé ainsi que les valeurs rapportés pour le CaCl 2 ·2H 2 O. Les spectres RMN-ES du 35 Cl sont aussi presentés pour le CaCl 2 ·6H 2 O et, lorsqu'on les compare, les observations relatives aux spectres RMN-ES du CaCl 2 , du CaCl 2 ·2H 2 O et du CaCl 2 ·6H 2 O démontrent clairement la sensibilité du GCE du chlore et des tenseurs du DC sur la symétrie locale et aux changements dans l'état d'hydratation. Par exemple, les valeurs de d iso diminuent avec une augmentation de l'hydratation. On a fait appel à des calculs selon la théorie de la fonctionnelle de la densité en utilisant une onde améliorée par un opérateur de projection comportant une jauge (« GIPAW-DFT ») pour corroborer les observations faites par RMN-ES, pour éliminer la présence d'autres hydrates dans nos échantil-lons, pour affiner les positions des atomes d'hydrogène dans le CaCl 2 ·2H 2 O et pour explorer la relation isostructurale entre le CaCl 2 et...

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Section: Solid-state 35/37 CL and 43 Ca Nmrmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A multinuclear solid-state magnetic resonance and GIPAW DFT study of anhydrous calcium chloride and its hydrates

Widdifield

Bryce

2011

Can. J. Chem.

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“…In general, the quadrupolar interaction for ionic chloride-containing systems is much lower than for the covalent chlorine systems, and thus 35/37 Cl SS-NMR spectroscopy has been an increasingly popular method for studying the environments of chloride ions in a variety of organic and inorganic materials over the past two decades. [19][20][21][22] However, it has recently been demonstrated that it is possible to acquire high-quality chlorine NMR spectra of compounds with covalently bound chlorine with relatively much larger C Q values. 23 Both the EFG and chemical shielding tensors are sensitive reporters on the local molecular and electronic structure, and as such 35/37 Cl SSNMR is a valuable tool for the characterization of chlorine containing compounds.…”

Section: Introductionmentioning

confidence: 99%

Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

et al. 2017

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Citation for published item:ohD ynd § rej nd rodgkinsonD ul nd iddi(eldD gory wF nd tesD tonthn F nd hr § ¡ %nsk¡ yD wrtin @PHIUA 9ixploring systemti disrepnies in hp lultions of hlorine nuler qudrupole ouplingsF9D tournl of physil hemistry eFD IPI @PIAF ppF RIHQERIIQF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. ABSTRACT: Previous studies revealed significant discrepancies between DFT-calculated and experimental nuclear quadrupolar coupling constants (C Q ) at chlorine atoms, particularly in ionic solids. Various aspects of the computations are systematically investigated here, including the choice of the DFT functional, basis set convergence, and geometry optimization protocol. The effect of fast (fs) time-scale dynamics are probed using molecular dynamics (MD) and nuclear quantum effects (NQEs) are considered using path-integral MD calculations. It is shown that the functional choice is the most important factor related to improving the accuracy of the 2 quadrupolar coupling calculations and functionals beyond the generalized gradient approximation (GGA) level, such as hybrid and meta-GGA functionals, are required for good correlations with experiment. The influence of molecular dynamics and NQEs is less important than the functional choice in the studied systems. A method which involves scaling the calculated quadrupolar coupling constant is proposed here; its application leads to good agreement with experimental data.

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“…1) have spin quantum numbers greater than 1/2 and are called quadrupolar nuclei. Indeed, the stable isotopes of chlorine, bromine, and iodine are all quadrupolar [28][29][30]. The NMR spectra of such nuclei are influenced by the interaction between the quadrupole moment of the nucleus (Q) and the electric field gradient (EFG) at the nucleus.…”

Section: The Nuclear Electric Quadrupolar Interactionmentioning

confidence: 99%

Solid-State NMR Study of Halogen-Bonded Adducts

Bryce

Viger‐Gravel

2014

Topics in Current Chemistry

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Nuclear magnetic resonance (NMR) spectroscopy offers unique insights into halogen bonds. NMR parameters such as chemical shifts, quadrupolar coupling constants, J coupling constants, and dipolar coupling constants are in principle sensitive to the formation and local structure of a halogen bond. Carrying out NMR experiments on halogen-bonded adducts in the solid state may provide several advantages over solution studies including (1) the absence of solvent which can interact with halogen bond donor sites and complicate spectral interpretation, (2) the lack of a need for single crystals or even long-range crystalline order, and (3) the potential to measure complete NMR interaction tensors rather than simply their isotropic values. In this chapter, we provide an overview of the NMR interactions and experiments which are relevant to the study of nuclei which are often found in halogen bonds (RX···Y) including (13)C, (35/37)Cl, (79/81)Br, (127)I, (77)Se, and (14/15)N. Experimental examples based on iodoperfluorobenzene halides, bis(trimethylammonium)alkane diiodide, and selenocyanate complexes, as well as haloanilinium halides, are discussed. Of particular interest is the sensitivity of the isotropic chemical shifts, the chemical shift tensor spans, and the halide nuclear electric quadrupolar coupling tensors to the halogen bond geometry in such compounds. Technical limitations associated with the NMR spectroscopy of covalently-bonded halogens are underlined.

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Solid-state NMR of quadrupolar halogen nuclei

Cited by 70 publications

References 156 publications

A multinuclear solid-state magnetic resonance and GIPAW DFT study of anhydrous calcium chloride and its hydrates

A multinuclear solid-state magnetic resonance and GIPAW DFT study of anhydrous calcium chloride and its hydrates

Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

Solid-State NMR Study of Halogen-Bonded Adducts

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