NMR spectroscopic study of xenon fluorides in the gas phase and of XeF2 in the solid state

Gerken, Michael; Hazendonk, Paul; Nieboer, Jared; Schrobilgen, Gary J.

doi:10.1016/j.jfluchem.2004.04.001

Cited by 35 publications

(36 citation statements)

References 29 publications

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“…47 The current ab initio result for σ F of ca. 166 ppm is also reasonably close to the solid-state NMR results of 125(5) ppm 46 and 150 (20) ppm. 48 Hence, through a combination of ab initio and DFT modeling we have achieved theoretical estimates of the shielding parameters in XeF 2 with a fairly good agreement with the experiment, especially for shielding anisotropies, reckoning with the experimental error limits.…”

Section: B Correlation Effects and Dft Performancesupporting

confidence: 79%

“…By using the present ab initio correlated CCSD(T)/AIV data for the NR part and CCSD/RAS data for the relativistic BPPT terms, combined with the basis set correction [FIVu2(Xe)→FIVu6(Xe)] estimated at the DFT/BHandHLYP level, as well as the present rovibrational correction at T = 300 K in the "Total" result in Table II, we obtain only slightly over-/underestimated σ F /σ Xe when compared with gas-phase experimental results. 46 Also the estimated non-rovibrationally corrected σ Xe of ca. 4173 ppm is close to the experimental solid state results 4260(10) ppm 46 and 4245(20) ppm, 48 differing slightly more from the NMR relaxation result in a solvent.…”

Section: B Correlation Effects and Dft Performancementioning

confidence: 99%

“…46 Also the estimated non-rovibrationally corrected σ Xe of ca. 4173 ppm is close to the experimental solid state results 4260(10) ppm 46 and 4245(20) ppm, 48 differing slightly more from the NMR relaxation result in a solvent. 47 The current ab initio result for σ F of ca.…”

Section: B Correlation Effects and Dft Performancementioning

confidence: 99%

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Rovibrational effects on NMR shieldings in a heavy-element system: XeF2

Lantto

Kangasvieri

Vaara

2012

The Journal of Chemical Physics

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Fully quantum-mechanical treatment of the effects of thermal rovibrational motion in a heavy-element molecule with relativistic effects is carried out for the heavy (129/131)Xe and light (19)F nuclear shieldings in the linear XeF(2) molecule. More importantly, purely quantum-mechanical, intramolecular phenomena, the primary and secondary isotope effect on these shieldings, respectively, are treated with including both the zero-point vibrational and finite-temperature effects. While large solvent effects influence the experimental absolute shielding constants and chemical shifts (thereby making comparison of experiment and theory very difficult), they are not significant for the isotope shifts. We study the role of electron correlation at both nonrelativistic (NR) and relativistic [Breit-Pauli perturbational theory (BPPT) as well as 4-component Dirac theory] level. We obtain quantitative agreement with the nearly solvent-independent experimental (19)F secondary isotope shifts. This implies a promising accuracy for our predictions of the experimentally so far non-existing primary Xe isotope shift and the temperature dependence of Xe and F chemical shifts corresponding to a low pressure gas phase. To achieve this, a combination of high-level ab initio NR shielding surface is found necessary, in the present work supplemented by relativistic corrections by density-functional theory (DFT). Large errors are demonstrated to arise due to DFT in the NR shielding surface, explaining findings in recent computational studies of heavy-element isotope shifts. Besides a high-quality property hypersurface, the inclusion of thermal effects (in addition to zero-point motion) is also necessary to compare with experimental results. The geometry dependence of the different relativistic influences on the wave function, Zeeman interaction, and hyperfine interaction, as well as their role in the temperature dependence of both the Xe and F shielding constants and their isotope shifts, are discussed. The relativistic rovibrational effects arise from the same individual contributions as previously found for the chemical shifts and shielding anisotropies. In general, the spin-orbit interactions are more sensitive to rovibrational motion than the scalar relativistic contributions. A previously suggested third-order BPPT contribution to shielding anisotropy is shown to be important for a better agreement with experiment.

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Section: B Correlation Effects and Dft Performancesupporting

confidence: 79%

Section: B Correlation Effects and Dft Performancementioning

confidence: 99%

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Rovibrational effects on NMR shieldings in a heavy-element system: XeF2

Lantto

Kangasvieri

Vaara

2012

The Journal of Chemical Physics

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“…[16,17] Theg as-phase 19 Fa nd 129 Xe NMR spectra of XeF 6 display broad singlets. [18] Prior to this work, no examples of Xe VI ÀNbonds had been reported. Aconsiderable number of Xe II ÀNs pecies in which Xe is bonded to sp-, sp 2 -, or sp 3hybridized Natoms are known, [19] whereas only three examples of Xe IV À Nb onds have been reported, [C 6 F 5 XeF 2 ][BF 4 ]· (NCCH 3 ) n (n = 1or2) [20] and F 2 OXeNCCH 3 .…”

mentioning

confidence: 99%

Syntheses and Structures of F₆XeNCCH₃ and F₆Xe(NCCH₃)₂

et al. 2015

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Acetonitrile and the potent oxidative fluorinating agent XeF 6 react at À40 8 8Ci nF reon-114 to form the highly energetic, shock-sensitive compounds F 6 XeNCCH 3 (1)a nd F 6 Xe(NCCH 3 ) 2 ·CH 3 CN (2·CH 3 CN). Their low-temperature single-crystal X-rays tructures show that the adducted XeF 6 molecules of these compounds are the most isolated XeF 6 moieties thus far encountered in the solid state and also providet he first examples of Xe VI ÀNb onds.T he geometry of the XeF 6 moiety in 1 is nearly identical to the calculated distorted octahedral (C 3v )geometry of gas-phase XeF 6 .The C 2v geometry of the XeF 6 moiety in 2 resembles the transition state proposed to account for the fluxionality of gas-phase XeF 6 . The energy-minimized gas-phase geometries and vibrational frequencies were calculated for 1 and 2,a nd their respective binding energies with CH 3 CN were determined. The Raman spectra of 1 and 2·CH 3 CN were assigned by comparison with their calculated vibrational frequencies and intensities.

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“…769 19 F and 129 Xe MAS NMR spectra for solid XeF 2 gave experimental values for 129 Xe and 19 F shielding anisotropies (4260 AE 10, 125 AE 5 ppm, respectively). 770 …”

Section: Group 18mentioning

confidence: 99%

Solid state NMR spectroscopy

Davidson¹

Spectroscopic Properties of Inorganic and Organometallic Compounds

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NMR spectroscopic study of xenon fluorides in the gas phase and of XeF2 in the solid state

Cited by 35 publications

References 29 publications

Rovibrational effects on NMR shieldings in a heavy-element system: XeF2

Rovibrational effects on NMR shieldings in a heavy-element system: XeF2

Syntheses and Structures of F₆XeNCCH₃ and F₆Xe(NCCH₃)₂

Solid state NMR spectroscopy

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NMR spectroscopic study of xenon fluorides in the gas phase and of XeF2 in the solid state

Cited by 35 publications

References 29 publications

Rovibrational effects on NMR shieldings in a heavy-element system: XeF2

Rovibrational effects on NMR shieldings in a heavy-element system: XeF2

Syntheses and Structures of F6XeNCCH3 and F6Xe(NCCH3)2

Solid state NMR spectroscopy

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Syntheses and Structures of F₆XeNCCH₃ and F₆Xe(NCCH₃)₂