The Hyperfine Structures of CuCl and CuBr in Their Ground States Studied by Microwave Fourier Transform Spectroscopy

doi:10.1006/jmsp.1993.1254

Journal of Molecular Spectroscopy

Volume 161, Issue 2, October 1993, Pages 499-510

https://doi.org/10.1006/jmsp.1993.1254 Get rights and content

Abstract

The hyperfine structure of the J = 1 ← 0 rotational transition of CuCl as well as the J = 3 ← 2, 2 ← 1, and 1 ← 0 rotational transitions of CuBr in the v = 0 vibrational level have been investigated using a microwave Fourier transform spectrometer. The molecules were produced by laser ablation of the copper halide followed by an axial supersonic expansion into a near-semiconfocal Fabry-Perot cavity. The analysis of the hyperfine structure yielded improved values of the rotational and electric quadrupole constants and determined the nuclear spin-rotation constants for the first time. The physical implications of these results are discussed.

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We review the solid-state NMR literature for the ^35/37Cl, ^79/81Br, and ¹²⁷I nuclides, with coverage up to August 2008. The theory related to NMR spectroscopy of half-integer quadrupolar nuclei in powdered samples is briefly summarized, as are the experimental methods for recording such spectra. The most recent experimental results demonstrate the increasing feasibility and utility of observing solid-state NMR spectra for these nuclei, particularly chlorine-35/37. Several chlorine chemical shift tensors have been measured recently, along with their orientation relative to the electric field gradient tensor. The increased availability of ultrahigh-field solid-state NMR spectrometers (B₀ ≥ 18.8 T) is the dominant factor responsible for the increased number of studies and increased amount of available information. For example, insights have been gained into the hydrogen bonding environment at the chlorine atoms in various organic hydrochloride salts by interpreting trends in the chlorine quadrupolar coupling and chemical shift tensors. The sensitivity of the ^35/37Cl NMR parameters to polymorphism and pseudo-polymorphism has also been demonstrated. Important advances in quantum chemistry which are having an impact on the computation of quadrupolar and magnetic shielding tensors for these nuclei are also briefly discussed. Data available from gas-phase molecular beam and microwave spectroscopy experiments are presented. Finally, prospects for future studies of ^35/37Cl, ^79/81Br, and ¹²⁷I by solid-state NMR spectroscopy are presented.
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The high-resolution pure rotational spectra of CuI and AgI have been reinvestigated in the frequency range 2.5–18 GHz using microwave Fourier transform spectroscopy. Gaseous samples of the diatomic metal iodides have been obtained by laser ablation of target rods made of suitable solid precursors. Improved rotational parameters, nuclear quadrupolar coupling constants, and spin–rotation interaction constants have been obtained, along with the first reported spin–spin coupling parameters for copper iodide. Information about the anisotropy of nuclear magnetic shielding and the indirect spin–spin coupling in the absence of intermolecular effects are derived from the high-resolution rotational spectroscopic data.
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Regular ArticleThe Hyperfine Structures of CuCl and CuBr in Their Ground States Studied by Microwave Fourier Transform Spectroscopy

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Regular Article
The Hyperfine Structures of CuCl and CuBr in Their Ground States Studied by Microwave Fourier Transform Spectroscopy