Anisotropy of the Fluorine Chemical Shift Tensor in Xenon Tetrafluoride

Blinc, R.; Zupančić, I.; Maričić, Siniša; Veksli, Zorica

doi:10.1063/1.1734592

Cited by 23 publications

(9 citation statements)

References 5 publications

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“…The difference in observed values of δ(F) iso between XeF 2 and XeF 4 , ≃ 180 ppm, agrees well with our calculated value, σ(F) iso ≃ 170 ppm. In addition, our calculated values of Ω(F) for XeF 4 are within this range of observed values. , Calculations were not carried out on XeF 6 because it exists as a tetramer in solution 79 and in the solid state the structure is complicated by the presence of nondiscrete polymeric units. , …”

Section: Resultssupporting

confidence: 77%

“…Jokisaari et al 24 used the method based on eq 3 to determine Ω(F), 205 ppm, for XeF 2 in acetonitrile. There have been experimental reports of Ω(F) for XeF 4 , ranging from 261 to 790 ppm, 90,91 and other main-group fluorides; solid-state 19 F NMR results indicate that for the series: SF 6 , SeF 6 , and TeF 6 , Ω(F) is 310, 370, and 215 ppm, respectively. 92 Experimental values of δ( 19 F) iso have previously been determined for XeF 2 , XeF 4 , and the XeF 6 -tetramer in solution: -199.6, -15.7, +118.3 ppm.…”

Section: Experimental and Computational Detailsmentioning

confidence: 99%

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Investigation of Magnetic Shielding in Xenon Difluoride Using Solid-State NMR Spectroscopy and Relativistic Density Functional Theory

2004

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The xenon and fluorine magnetic shielding tensors, σ, of XeF 2 are characterized using solid-state 129 Xe and 19 F NMR spectroscopy and nonrelativistic and spin-orbit relativistic zeroth-order regular approximation density functional theory (ZORA DFT). Analysis of 129 Xe and 19 F NMR spectra acquired with magic-angle spinning at several spinning rates indicates that the Xe and F magnetic shielding tensors are axially symmetric, as dictated by the crystal symmetry. The isotropic 129 Xe chemical shift is -1603 ( 5 ppm with respect to OXeF 4 (neat liquid, 24 °C) and the Xe magnetic shielding anisotropy, Ω, is 4245 ( 20 ppm, the first anisotropy measured directly for a xenon compound. The parallel component of the experimentally determined xenon chemical shift tensor, δ | ) -4433 ppm differs from δ(Xe(free atom)) by ∼1000 ppm, providing the first experimental demonstration that relativistic effects play an important role in the nuclear magnetic shielding for xenon. Both the sign and magnitude of the isotropic indirect 129 Xe, 19 F nuclear spin-spin coupling constant are determined, -5560 ( 50 Hz. Analysis of the 19 F NMR spectra yield Ω(F) ) 150 ( 20 ppm. The ZORA DFT method has been employed to calculate σ(Xe) and σ(F) for isolated XeF 2 and XeF 4 molecules, as well as σ(Kr) and σ(F) for an isolated KrF 2 molecule, at the relativistic and nonrelativistic levels of theory. Spinorbit relativistic DFT results for Ω(Xe) are in very good agreement with those determined experimentally and highlight the importance of relativistic effects.

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Section: Resultssupporting

confidence: 77%

Section: Experimental and Computational Detailsmentioning

confidence: 99%

Investigation of Magnetic Shielding in Xenon Difluoride Using Solid-State NMR Spectroscopy and Relativistic Density Functional Theory

2004

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“…(1) and (3), respectively. In addition, the total absolute shielding may be expressed as (4) From the shape of the higher temperature resonance in Fig. 2 With Eqs.…”

Section: Discussionmentioning

confidence: 99%

Magnetic Shielding of 19F in XeF4

Hindermann¹,

Falconer²

1970

The Journal of Chemical Physics

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The second moment of the 19F nuclear magnetic resonance of XeF4 has been measured as a function of temperature and of magnetic field both in the rigid lattice and above a motional transition. A completely general shielding tensor was determined indicating that the previous assumption of axial symmetry about the Xe–F bonds was an oversimplification. The out-of-plane component σx was determined uniquely to be 0 ± 8 × 10−6, referred to the bare 19F nucleus. Complementary pairs of values for the in-plane shielding were found to be σy(σz) = 394 ± 25 × 10−6and σz(σy) = 261 ± 25 × 10−6. As for XeF2, the field-independent rigid-lattice second moment is larger than that calculated from the average atom positions.

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“…17) and the overlap integral is given by S(i,j) = <u,|u,) (Eq. 18) The total orbital energy is then e = mrEr (Eq. 19) where mr is the occupation number of the rth molecular orbital.…”

Section: The Molecular Orbital Modelmentioning

confidence: 99%