Hyperfine Structure of HD17O by Beam-Maser Spectroscopy

Verhoeven, J.; Dymanus, A.; Bluyssen, H.

doi:10.1063/1.1671557

Cited by 135 publications

(44 citation statements)

References 18 publications

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“…with the free D20 value of 307 kHz (Verhouven, Dymanus & Bluyssen, 1969). Also the experimental downshift is well reproduced by our calculations, because the free-water quadrupole coupling constant is -325 kHz at the 8-41 lg** level, i.e.…”

Section: Quadrupole Coupling Constantssupporting

confidence: 66%

Structural, vibrational and electronic properties of a crystalline hydrate from ab initio periodic Hartree–Fock calculations

Ojamäe¹,

Hermansson²,

Pisani³

et al. 1994

Acta Crystallogr Sect B

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The hydrate crystal lithium hydroxide monohydrate LiOH.H20 has been studied by ab initio periodic Hartree-Fock calculations. The influence of the crystalline environment on the local molecular properties (molecular geometry, atomic charges, electron density, molecular vibrations and deuterium quadrupole coupling constants) of the water molecule, the lithium and hydroxide ions has been calculated. A number of crystalline bulk properties are also presented; optimized crystalline structure, lattice energy and electronic band structure. The optimized cell parameters from calculations with a large basis set of triple-zeta quality differ by only 1-3% from the experimental neutron-determined cell, whereas the STO-3g basis set performs poorly (differences of 5-10%). With the triple-zeta basis also the atomic positions and intermolecular distances agree very well with the experiment. The lattice energy differs by -8% from the experimental value, and by at most 3% when a density-functional electron correlation correction is applied. Large electron-density rearrangements occur in the water molecule and in the hydrogen bond and are in qualitative and quanti-© 1994 International Union of Crystallography Printed in Great Britain -all rights reserved tative agreement with experimental X-ray diffraction results. The quadrupole-coupling constants of the water and hydroxide deuterium atoms are found to be very sensitive to the O---H bond length and are in good agreement with experimental values when the calculation is based on the experimental structure. The anharmonic O--H stretching vibrations in the crystal are presented and found to be very close to results from calculations on molecular clusters. The electronic band and density-of-states spectra are discussed. Model calculations on a hydrogen fluoride chain were used to rationalize the results. IntroductionThe water molecule and its unique binding properties are of interest to both experimentalists and theoreticians. Crystalline hydrates have consequently been extensively characterized experimentally. The effect of the crystalline environment on the structure, vibrations, electron density, quadrupolar coupling constants etc. of the water molecule have been investigated in many hundreds of diffraction and spectroscopic studies (e.g. Falk & Knop, 1973; Acta Crvstallographica Section B ISSN 0108-7681 ©i994 LARS OJAMAE et al. 269 Olovsson & J6nsson, 1976; Berglund, Lindgren & Tegenfeldt, 1978a,b; Chiari & Ferraris, 1982;Hermansson, 1984;Mikenda, 1986;Lutz, 1988). Among the crystalline hydrates one finds examples of a wide variety of water environments, from very weakly to very strongly bound molecules. This is reflected in the broad ranges of measured H-..O hydrogen-bond distances (from, say, 3.2 down to 1.65 A0, OH vibrational frequency downshifts (from -150 to --1000 cm-~) and deuteron quadrupole coupling constants (from 240 down to -170 kHz for the most strongly bound water molecules).The theoretical approach to the study of hydrates has commonly been to use q...

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Section: Quadrupole Coupling Constantssupporting

confidence: 66%

Structural, vibrational and electronic properties of a crystalline hydrate from ab initio periodic Hartree–Fock calculations

Ojamäe¹,

Hermansson²,

Pisani³

et al. 1994

Acta Crystallogr Sect B

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“…The 17 O QCC is determined by the electron distribution around the water oxygen and, hence, is affected by hydrogen-bond-induced electronic polarization (Cummins et al, 1985). The values for x I in ice Ih, liquid, and vapour are, respectively, 6.5 MHz (Spiess et al, 1969;Edmonds & Zussman, 1972), 8.1 MHz (van der Maarel et al, 1985Struis et al, 1987;Eggenberger et al, 1993), and 10.2 MHz (Verhoeven et al, 1969). An estimate of the 17 O QCC for the internal water molecules of BPTI may be obtained as follows.…”

Section: Internal Watermentioning

confidence: 99%

Protein Hydration Dynamics in Aqueous Solution: A Comparison of Bovine Pancreatic Trypsin Inhibitor and Ubiquitin by Oxygen-17 Spin Relaxation Dispersion

Денисов

Halle

1995

Journal of Molecular Biology

162

177

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Water oxygen-17 spin relaxation was used to study hydration and dynamics Condensed Matter Magnetic Resonance Group, Chemical of the globular proteins bovine pancreatic trypsin inhibitor (BPTI) and ubiquitin in aqueous solution. The frequency dispersion of the longitudinal Center, Lund University P. O. Box 124, S-22100 Lund and transverse relaxation rates was measured over the Larmor frequency Sweden range 2.6 to 49 MHz in the pD range 2 to 11 at 27°C. While the protein-induced relaxation enhancement was similar for the two proteins at high frequencies, it was an order of magnitude smaller for ubiquitin than for BPTI at low frequencies. This difference was ascribed to the abscence, in ubiquitin, of highly ordered internal water molecules, which are known to be present in BPTI and in most other globular proteins. These observations demonstrate that the water relaxation dispersion in protein solutions is essentially due to a few structural water molecules buried within the protein matrix, but exchanging rapidly with the external water. The relaxation data indicate that the internal water molecules of BPTI exchange with bulk water on the time-scale 10 −8 to 10 −6 second thus lowering the recently reported upper bound on the residence time of these internal water molecules by four orders of magnitude, and implying that local unfolding occurs on the submicrosecond time-scale. The water molecules residing at the surface of the two proteins were found to be highly mobile, with an average rotational correlation time of approximately 20 picoseconds. For both proteins, the oxygen-17 relaxation depended only very weakly on pD, showing that ionic residues do not perturb hydration water dynamics more than other surface residues. We believe that the present results resolve the long-standing controversy regarding the mechanism behind the spin relaxation dispersion of water nuclei in protein solutions, thus establishing oxygen-17 relaxation as a powerful tool for studies of structurally and functionally important water molecules in proteins and other biomolecules.

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“…The largest components of the EFG tensors, eq zz , are multiplied by the best known value for the deuteron nuclear quadrupole moment [48] leading to the c D values given in Table 2. The c D association shifts represent the differences to the calculated and measured D 2 O monomer values [49] (Figure 6). As found for the frequencies, the association shifts for c D of fully H-bonded D 2 O in DMSO (structure D) are comparable to that of liquid bulk water.…”

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confidence: 99%

Structure and Dynamics of Water Confined in Dimethyl Sulfoxide

Wulf

Ludwig

2006

ChemPhysChem

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We study the structure and dynamics of hydrogen-bonded complexes of H2O/D2O and dimethyl sulfoxide (DMSO) by infrared spectroscopy, NMR spectroscopy and ab initio calculations. We find that single water molecules occur in two configurations. For one half of the water monomers both OH/OD groups form strong hydrogen bonds to DMSO molecules, whereas for the other half only one of the two OH/OD groups is hydrogen-bonded to a solvent molecule. The H-bond strength between water and DMSO is in the order of that in bulk water. NMR deuteron relaxation rates and calculated deuteron quadrupole coupling constants yield rotational correlation times of water. The molecular reorientation of water monomers in DMSO is two-and-a-half times slower than in bulk water. This result can be explained by local structure behavior.

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Hyperfine Structure of HD17O by Beam-Maser Spectroscopy

Cited by 135 publications

References 18 publications

Structural, vibrational and electronic properties of a crystalline hydrate from ab initio periodic Hartree–Fock calculations

Structural, vibrational and electronic properties of a crystalline hydrate from ab initio periodic Hartree–Fock calculations

Protein Hydration Dynamics in Aqueous Solution: A Comparison of Bovine Pancreatic Trypsin Inhibitor and Ubiquitin by Oxygen-17 Spin Relaxation Dispersion

Structure and Dynamics of Water Confined in Dimethyl Sulfoxide

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