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Title: Semi-empirical refinements of crystal structures using 17 O quadrupolar-coupling tensors

ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA
  2. Department of Chemistry, Washington and Jefferson College, Washington, Pennsylvania 15301, USA
  3. Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA, Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, USA
Publication Date:
Sponsoring Org.:
OSTI Identifier:
Grant/Contract Number:
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 6; Related Information: CHORUS Timestamp: 2018-02-14 19:56:57; Journal ID: ISSN 0021-9606
American Institute of Physics
Country of Publication:
United States

Citation Formats

Holmes, Sean T., Iuliucci, Robbie J., Mueller, Karl T., and Dybowski, Cecil. Semi-empirical refinements of crystal structures using 17 O quadrupolar-coupling tensors. United States: N. p., 2017. Web. doi:10.1063/1.4975170.
Holmes, Sean T., Iuliucci, Robbie J., Mueller, Karl T., & Dybowski, Cecil. Semi-empirical refinements of crystal structures using 17 O quadrupolar-coupling tensors. United States. doi:10.1063/1.4975170.
Holmes, Sean T., Iuliucci, Robbie J., Mueller, Karl T., and Dybowski, Cecil. Tue . "Semi-empirical refinements of crystal structures using 17 O quadrupolar-coupling tensors". United States. doi:10.1063/1.4975170.
title = {Semi-empirical refinements of crystal structures using 17 O quadrupolar-coupling tensors},
author = {Holmes, Sean T. and Iuliucci, Robbie J. and Mueller, Karl T. and Dybowski, Cecil},
abstractNote = {},
doi = {10.1063/1.4975170},
journal = {Journal of Chemical Physics},
number = 6,
volume = 146,
place = {United States},
year = {Tue Feb 14 00:00:00 EST 2017},
month = {Tue Feb 14 00:00:00 EST 2017}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4975170

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Cited by: 4works
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  • A single crystal {sup 71}Ga NMR study of the garnet Y{sub 3}Ga{sub 5}O{sub 12} (YGG) has resulted in the determination of the first chemical shielding tensors reported for the {sup 71}GA quadrupole. The single-crystal spectra are analyzed in terms of the combined effect of quadrupole coupling and chemical shielding anisotropy (CSA). {sup 71}Ga quadrupole coupling and CSA parameters for the two (tetrahedrally and octahedrally coordinated) gallium sites with axial symmetry in YGG (Ga{sub IV}, C{sub Q} = 13.1 {+-} 0.2 MHz and {delta}{sub {sigma}} = 54 {+-} 50 ppm; Ga{sub VI}, C{sub Q} = 4.10 {+-} 0.06 MHz and {delta}{submore » {sigma}} = 24 {+-} 3 ppm) are fully consistent with its cubic crystal structure which supports the reliability of the experimental data. In addition, the {sup 71}Ga and {sup 27}Al isotropic chemical shifts for YGG and YAG give further support to the linear correlation observed earlier between {sup 71}Ga and {sup 27}Al isotropic chemical shifts. 52 refs., 5 figs., 2 tabs.« less
  • The orientation of the {sup 113}Cd chemical shielding tensors in single crystals of the dimer of diaquobis(2-hydroxybenzoato)cadmium(II), i.e. Cd-salicylate, and tetrakis(4-picoline)(nitrato-O,O{prime})(nitrato-O)cadmium(II), i.e. Cd-picoline, has been determined. The isotropic chemical shift was determined to be {minus}31 ppM for Cd-salicylate and +11 ppM for Cd-picoline. The space group symmetry of the Cd-salicylate crystal generates two magnetically distinct cadmium lattice sites. The assignment of each experimentally determined tensor to its respective lattice site was not possible due to the special geometry of the ligands in the lattice, which is discussed in the text. However, the two possible orientations differ only slightly and itmore » is therefore possible to interpret the orientation with respect to the ligand identity and geometry. In either case, the most deshielded element is oriented nearly perpendicular to a plane containing two water oxygen atoms. The most shielded element is oriented nearly perpendicular to a pentagonal best least-squares (BLS) plane defined by two pairs of bidentate benzoate oxygen atoms and one monodentate benzoate oxygen atom. The crystal of Cd-picoline generates two crystallographically distinct cadmium sites in the lattice. Two methods were used independently to assign the two experimentally determined tensors to each lattice site. 22 refs., 12 figs., 5 tabs.« less
  • The authors have obtained the oxygen-17 nuclear magnetic resonance (NMR) spectra of a variety of C{sup 17}O-labeled heme proteins, including sperm whale (Physeter catodon) myoglobin, two synthetic sperm whale myoglobin mutants (His E7 {yields} Val E7; His E7 {yields} Phe E7), adult human hemoglobin, rabbit (Oryctolagus cuniculus) hemoglobin, horseradish (Cochlearia armoracia) peroxidase isoenzymes A and C, and Caldariomyces fumago chloroperoxidase, in some cases as a function of pH, and have determined their isotropic {sup 17}O NMR chemical shifts, {delta}{sub i}, and spin-lattice relaxation times, T{sub 1}. They have also obtained similar results on a picket fence prophyrin. The results showmore » an excellent correlation between the infrared C-O vibrational frequencies, {nu}(C-O), and {delta}{sub i}, between {nu}(C-O) and the {sup 17}O nuclear quadrupole coupling constant, and as expected between e{sup 2}qQ/h and {delta}{sub i}. The results suggest the IR and NMR measurements reflect the same interaction, which is thought to be primarily the degree of {pi}-back-bonding from Fe d to CO {pi}* orbitals, as outlined previously.« less
  • The quadrupolar and chemical shift tensors, as well as the relative orientation of the two principle axis systems, are accurately determined using a two-dimensional nuclear magnetic resonance technique. Good agreement between experimental and simulated two-dimensional spectra is obtained for a series of rubidium and sodium compounds at multiple magnetic field strengths. Extension of this technique to correlate the quadrupolar and dipolar interactions, as well as the incorporation of a purely isotropic dimension resulting in a three-dimensional experiment is also discussed. {copyright} {ital 1996 American Institute of Physics.}
  • The effect of the oxygen-atom vacancies on the crystal structure of YBa/sub 2/Cu/sub 3/O/sub 7/minus/y/ has been investigated by performing empirical atom-atom potential calculations. Efforts were made to gain insight into the role of oxygen-atom vacancies in lowering the superconducting transition temperature, T/sub c/, of YBa/sub 2/Cu/sub 3/O/sub 7/minus/y/. The important structural characteristics of YBa/sub 2/Cu/sub 3/O/sub 7/minus/y/ as determined by extensive powder neutron diffraction measurements are reported. Then these experimental observations are simulated in terms of atom-atom potentials, and the implications of the reported results concerning the high-T/sub c/ superconductivity observed for the studied complex are discussed. 30 refs.,more » 9 figs., 3 tabs.« less