B3LYP Calculation of Deuterium Quadrupole Coupling Constants in Molecules

Bailey, William C.

doi:10.1006/jmsp.1998.7604

Cited by 35 publications

(23 citation statements)

References 63 publications

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“…This was attributed to a combination of such factors as the neglect of vibrational averaging, limitations in the basis sets used, and errors in the experimental values. Bailey [20] quotes a value for the ratio q aa (k)/V aa (k) of 636.5 kHz/a.u, which gives a good fit to the experimental values for a wide range of molecules when using B3LYP/6-31G**.…”

Section: Deuterium Quadrupolar Tensorsmentioning

confidence: 96%

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

Emsley

Lesage

et al. 2007

Liquid Crystals

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The conformational distributions in molecules that form liquid crystalline phases are predicted to depend strongly on orientational order. Results are presented here to test this hypothesis. The mesogen 4-hexyloxy-49-cyanobiphenyl (6OCB) has been studied by NMR spectroscopy in the isotropic phase and in the nematic phase. In the isotropic phase the fieldinduced orientational ordering produces small dipolar couplings between 13 C and 1 H nuclei, which were determined from the 13 C spectra. Couplings between 1 H nuclei were also obtained using 2D selective refocusing experiments. In the nematic phase, both 1 H-1 H dipolar couplings and quadrupolar splittings for deuterium nuclei were measured for partiallydeuterated samples. Both proton and deuterium spectra were also obtained for 6OCB in an equimolar mixture with 4-(ethoxybenzylidene)-49-butylaniline (EBBA). This mixture exhibits SmA and SmB phases. The data obtained from these experiments has been analysed to yield the probability distribution of the conformations in this molecule generated by rotations about bonds. It is found that there is a substantial influence of the orientational order of the molecules on these distributions.

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Section: Deuterium Quadrupolar Tensorsmentioning

confidence: 96%

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

Emsley

Lesage

et al. 2007

Liquid Crystals

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“…DFT (B3LYP/6-31G) computations of deuterium quadrupolar parameters in organic molecules 14 15 Finally, the DFT (B3LYP) data computed for classical transition metal hydrides 5 (using the LANL2DZ basis set for metal atoms and 6-31G for other atoms) with full optimizations of geometries are also overestimated ( Table 2). It is likely that this situation is associated with the high sensitivity of the DQCC to the computed X-D bonds lengths.…”

Section: Quadrupolar Coupling In Dihydrogen Complexes From Quantum Chmentioning

confidence: 98%

“…It is likely that this situation is associated with the high sensitivity of the DQCC to the computed X-D bonds lengths. 14,15 The fast-spinning nature of the D 2 ligand in RuD D 2 pp 3…”

Section: Quadrupolar Coupling In Dihydrogen Complexes From Quantum Chmentioning

confidence: 99%

Orientations of the principal components of electric field gradients and internal motions in dihydrogen ligands from the ²H T₁ NMR relaxation data in solution

Bakhmutov

2003

Magnetic Reson in Chemistry

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The deuterium spin-lattice relaxation times in (D2) ligands of W, Ru and Os complexes are reviewed and analyzed in terms of the fast internal (D2) motions: free rotation, librations and 180 degrees jumps. The analysis was performed using quadrupolar coupling constant (DQCC) parameters taken from the solid-state 2H NMR spectra and density function theory calculations. It is shown that the calculated DQCC values can be corrected for further use in interpretations of deuterium relaxation times for Ru and Os dihydrogen complexes. The resulting data led to a criterion for using the relaxation data to distinguish fast-spinning dihydrogen ligands. It is shown that the principal components of electric field gradient tensors at D in the dihydrogen ligands are oriented closer to M-D directions.

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“…The difference between the observed splittings from the 13 Initially a difference between the coupling constant CD q for deuterium bonded to 12 C and 13 C, i.e., different C-D bond lengths [19][20][21], was considered to be a potential source of ( ) ν Δ Δ . We also considered the effect of a single 13 C on the molecular magnetizability tensor and its putative influence on the molecular order tensor (see SI Section 1).…”

Section: 3mentioning

confidence: 99%

Benzene at 1GHz. Magnetic field-induced fine structure

Heist

Poon

Samulski

et al. 2015

Journal of Magnetic Resonance

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The deuterium NMR spectrum of benzene-d 6 in a high field spectrometer (1 GHz protons) exhibits a magnetic field-induced deuterium quadrupolar splitting ν Δ . The magnitude of ν Δ observed for the central resonance is smaller than that observed for the 13 C satellite doublets ν ′ Δ . This difference,, is due to unresolved fine structure contributions to the respective resonances. We determine the origins of and simulate this difference, and report pulse sequences that exploit the connectivity of the peaks in the 13 C and 2 H spectra to determine the relative signs of the indirect coupling, CD

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B3LYP Calculation of Deuterium Quadrupole Coupling Constants in Molecules

Cited by 35 publications

References 63 publications

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

Orientations of the principal components of electric field gradients and internal motions in dihydrogen ligands from the ²H T₁ NMR relaxation data in solution

Benzene at 1GHz. Magnetic field-induced fine structure

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B3LYP Calculation of Deuterium Quadrupole Coupling Constants in Molecules

Cited by 35 publications

References 63 publications

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

The structure and conformation of a mesogenic compound between almost zero and almost complete orientational order

Orientations of the principal components of electric field gradients and internal motions in dihydrogen ligands from the 2H T1 NMR relaxation data in solution

Benzene at 1GHz. Magnetic field-induced fine structure

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Orientations of the principal components of electric field gradients and internal motions in dihydrogen ligands from the ²H T₁ NMR relaxation data in solution