The hyperfine structure in the rotational spectra of D{sub 2}{sup 17}O and HD{sup 17}O: Confirmation of the absolute nuclear magnetic shielding scale for oxygen

Journal Article · Sat Mar 28 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4916068· OSTI ID:22415565

Puzzarini, Cristina; Cazzoli, Gabriele ^[1]; Harding, Michael E. ^[2]; Vázquez, Juana ^[3]; Gauss, Jürgen ^[4]

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1. Dipartimento di Chimica “Giacomo Ciamician,” Università degli Studi di Bologna, Via Selmi 2, I-40126 Bologna (Italy)
2. Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Postfach 3640, D-76021 Karlsruhe (Germany)
3. Center for Theoretical Chemistry, Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712 (United States)
4. Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz (Germany)

Guided by theoretical predictions, the hyperfine structures of the rotational spectra of mono- and bideuterated-water containing {sup 17}O have been experimentally investigated. To reach sub-Doppler resolution, required to resolve the hyperfine structure due to deuterium quadrupole coupling as well as to spin-rotation (SR) and dipolar spin-spin couplings, the Lamb-dip technique has been employed. The experimental investigation and in particular, the spectral analysis have been supported by high-level quantum-chemical computations employing coupled-cluster techniques and, for the first time, a complete experimental determination of the hyperfine parameters involved was possible. The experimentally determined {sup 17}O spin-rotation constants of D{sub 2}{sup 17}O and HD{sup 17}O were used to derive the paramagnetic part of the corresponding nuclear magnetic shielding constants. Together with the computed diamagnetic contributions as well as the vibrational and temperature corrections, the latter constants have been employed to confirm the oxygen nuclear magnetic shielding scale, recently established on the basis of spin-rotation data for H{sub 2}{sup 17}O [Puzzarini et al., J. Chem. Phys. 131, 234304 (2009)].

• OSTI ID: 22415565
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CALCULATION METHODS
CORRECTIONS
DEUTERATION
DIAMAGNETISM
HEAVY WATER
HYPERFINE STRUCTURE
MAGNETIC SHIELDING
OXYGEN
OXYGEN 17
PARAMAGNETISM
RESOLUTION
ROTATIONAL STATES
SPIN