Nuclear Magnetic Resonance Shifts Research Articles

Intramolecular O-H⋯O and C-H⋯O hydrogen bond cooperativity in D-glucopyranose and D-galactopyranose-A DFT/GIAO, QTAIM/IQA, and NCI approach.

Density functional theory calculations are used to compute proton nuclear magnetic resonance (NMR) chemical shifts, interatomic distances, atom-atom interaction energies, and atomic charges for partial structures and conformers of α-D-glucopyranose, β-D-glucopyranose, and α-D-galactopyranose built up by introducing OH groups into 2-methyltetrahydropyran stepwisely. For the counterclockwise conformers, the most marked effects on the NMR shift and the charge on the OH1 proton are produced by OH2, those of OH3 and OH4 being somewhat smaller. This argues for a diminishing cooperative effect. The effect of OH6 depends on the configuration of the hydroxymethyl group and the position, axial or equatorial, of OH4, which controls hydrogen bonding in the 1,3-diol motif. Variations in the interaction energies reveal that a "new" hydrogen bond is sometimes formed at the expense of a preexisting one, probably due to geometrical constraints. Whereas previous work showed that complexing a conformer with pyridine affects only the nearest neighbour, successive OH groups increase the interaction energy of the N⋯H1 hydrogen bond and reduce its length. Analogous results are obtained for the clockwise conformers. The interaction energies for C-H⋯OH hydrogen bonding between axial CH protons and OH groups in certain conformers are much smaller than for O-H⋯OH bonds but they are largely covalent, whereas those of the latter are predominantly coulombic. These interactions are modified by complexation with pyridine in the same way as O-H⋯OH interactions: the computed NMR shifts of the CH protons increase, the atom-atom distances are shorter, and interaction energies are enhanced.

Pressure dependence of coherence-incoherence crossover behavior in KFe2As2 observed by resistivity and As75 -NMR/NQR

We present the results of $^{75}$As nuclear magnetic resonance (NMR), nuclear quadrupole resonance (NQR), and resistivity measurements in KFe$_2$As$_2$ under pressure ($p$). The temperature dependence of the NMR shift, nuclear spin-lattice relaxation time ($T_1$) and resistivity show a crossover between a high-temperature incoherent, local-moment behavior and a low-temperature coherent behavior at a crossover temperature ($T^*$). $T^*$ is found to increase monotonically with pressure, consistent with increasing hybridization between localized $3d$ orbital-derived bands with the itinerant electron bands. No anomaly in $T^*$ is seen at the critical pressure $p_{\rm c}=1.8$ GPa where a change of slope of the superconducting (SC) transition temperature $T_{\rm c}(p)$ has been observed. In contrast, $T_{\rm c}(p)$ seems to correlate with antiferromagnetic spin fluctuations in the normal state as measured by the NQR $1/T_1$ data, although such a correlation cannot be seen in the replacement effects of A in the AFe$_2$As$_2$ (A= K, Rb, Cs) family. In the superconducting state, two $T_1$ components are observed at low temperatures, suggesting the existence of two distinct local electronic environments. The temperature dependence of the short $T_{\rm 1s}$ indicates nearly gapless state below $T_{\rm c}$. On the other hand, the temperature dependence of the long component 1/$T_{\rm 1L}$ implies a large reduction in the density of states at the Fermi level due to the SC gap formation. These results suggest a real-space modulation of the local SC gap structure in KFe$_2$As$_2$ under pressure.

Molecular structure, the effect of solvent on UV–vis and NMR, FT–IR and FT–Raman spectra, NBO, frontier molecular orbital analysis of Mitomycin anticancer drug

In this study, the structural and spectral properties of anticancer drug ((1aR, 8R, 8as, 8bR)-6-amino-8a-methoxy-5-methyl-4,7-dioxo-1,1a,2,4,7,8,8a,8b-octahydroazirino[2′,3′:3,4]pyrrolo [1,2-a]indol-8-yl)methylcarbamate that is known as the brand of Mitomycin was analyzed by computational methods of Moller–Plesset (MP2) with the LanL2DZ and LanL2MB basis sets. First, the structure of desired material was drawn using Chembio Draw Ultra software and was optimized using Gaussian 09 software. The bond length (Ȧ) and bond angle (°) were measured by computational methods. Nuclear Magnetic Resonance (NMR) was calculated in the presence of polar and nonpolar solvents to determine the chemical shifts of 13C NMR and 1H NMR. Also these values were calculated using Chembio Draw Ultra software and were compared with measured values by Gaussian 09 software. Natural Bond Orbital (NBO) and UV–vis spectrum calculated by CIS–MP2/LanL2MB were used to determine the type of transfers between the electron levels and energy gap for these electron levels was determined by electron transfers of the highest occupied molecular orbital (HOMO) and the Lowest unoccupied molecular orbital (LUMO). Fourier Transform Infrared (FT–IR) and Fourier Transform Raman (FT–Raman) were used to identify functional groups and the type of normal vibrational mode and frequency range of bonds.

Computer-Guided Total Synthesis of Natural Products. Recent Examples and Future Perspectives

Quantum chemical calculations of nuclear magnetic resonance (NMR) shifts and coupling constants have been extensively employed in recent years mainly to facilitate structural elucidation of organic molecules. When the results of such calculations are used to determine the most likely structure of a natural product in advance, guiding the subsequent synthetic work, the term “computer-guided synthesis” could be coined. This review article describes the most relevant examples from recent literature, highlighting the scope and limitations of this merged computational/experimental approach as well.

(+)-BINOL and Pure Shift Experiment: A Bidirectional Approach for NMR Chiral Discrimination of Overcrowded Spectra of Primary Amines

In this work, enantiopure 1,1’-bi-2-naphthol (BINOL) derivatives and carboxylic acids were evaluated as chiral solvating agents (CSAs) in the nuclear magnetic resonance (NMR) chiral discrimination of primary amines. Among the CSAs screened, the readily available (+)-BINOL revealed a simple and rapid chiral auxiliary for 1H NMR chiral discrimination. The procedure required few minutes, assigning of the absolute configuration. The protocol was improved using the 1H pure shift pulse sequence for overcrowded alkyl primary amines due to the absence of JHH couplings. The 1H pure shift NMR experiment and the readily available (+)-BINOL chiral auxiliary can be used for routine chiral discrimination analysis of complex NMR spectra.

First-principles calculation study of electronic structures and magnetic properties of Mn-doped perovskite crystals for solar cell applications

The electronic structures and magnetic properties of manganese (Mn)-doped formamidinium lead halide perovskite compounds (FAPbI3, where FA = NH2CHNH2+) were investigated for solar cell application. The effects of Mn doping into FAPbI3 crystals on electronic structures, chemical shifts in nuclear magnetic resonance, and optical absorption spectra were studied by first-principles calculation on the basis of the density functional theory. The electron density distribution of the 6p orbital was delocalized on an iodine atom at the highest occupied molecular orbital, and that of the 3d orbital was localized on a Mn atom at the lowest unoccupied molecular orbital. The absorption properties in the near-infrared region originated from the first excitation process of ligand-metal charge transfer (LMCT). The chemical shifts of I-NMR and the g-tensor of Mn ions were associated with nuclear quadrupole interactions based on an electron field gradient and asymmetry parameters. The combination of LMCT with magnetic interactions is important for developing photovoltaic solar cells with a broad-band optical absorption spectrum in the near-infrared region.

Large-Scale Computation of Nuclear Magnetic Resonance Shifts for Paramagnetic Solids Using CP2K.

Large-scale computations of nuclear magnetic resonance (NMR) shifts for extended paramagnetic solids (pNMR) are reported using the highly efficient Gaussian-augmented plane-wave implementation of the CP2K code. Combining hyperfine couplings obtained with hybrid functionals with g-tensors and orbital shieldings computed using gradient-corrected functionals, contact, pseudocontact, and orbital-shift contributions to pNMR shifts are accessible. Due to the efficient and highly parallel performance of CP2K, a wide variety of materials with large unit cells can be studied with extended Gaussian basis sets. Validation of various approaches for the different contributions to pNMR shifts is done first for molecules in a large supercell in comparison with typical quantum-chemical codes. This is then extended to a detailed study of g-tensors for extended solid transition-metal fluorides and for a series of complex lithium vanadium phosphates. Finally, lithium pNMR shifts are computed for Li3V2(PO4)3, for which detailed experimental data are available. This has allowed an in-depth study of different approaches (e.g., full periodic versus incremental cluster computations of g-tensors and different functionals and basis sets for hyperfine computations) as well as a thorough analysis of the different contributions to the pNMR shifts. This study paves the way for a more-widespread computational treatment of NMR shifts for paramagnetic materials.

Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy

Facet engineering of oxide nanocrystals represents a powerful method for generating diverse properties for practical and innovative applications. Therefore, it is crucial to determine the nature of the exposed facets of oxides in order to develop the facet/morphology–property relationships and rationally design nanostructures with desired properties. Despite the extensive applications of electron microscopy for visualizing the facet structure of nanocrystals, the volumes sampled by such techniques are very small and may not be representative of the whole sample. Here, we develop a convenient 17O nuclear magnetic resonance (NMR) strategy to distinguish oxide nanocrystals exposing different facets. In combination with density functional theory calculations, we show that the oxygen ions on the exposed (001) and (101) facets of anatase titania nanocrystals have distinct 17O NMR shifts, which are sensitive to surface reconstruction and the nature of the steps on the surface. The results presented here open up methods for characterizing faceted nanocrystalline oxides and related materials.

Contrasting Phenomenology of NMR Shifts in Cuprate Superconductors

Nuclear magnetic resonance (NMR) shifts, if stripped of their uncertainties, must hold key information about the electronic fluid in the cuprates. The early shift interpretation that favored a single-fluid scenario will be reviewed, as well as recent experiments that reported its failure. Thereafter, based on literature shift data for planar Cu, a contrasting shift phenomenology for cuprate superconductors is developed, which is very different from the early view while being in agreement with all published data. For example, it will be shown that the hyperfine scenario used up to now is inadequate as a large isotropic shift component is discovered. Furthermore, the changes of the temperature dependences of the shifts above and below the superconducting transitions temperature proceed according to a few rules that were not discussed before. It appears that there can be substantial spin shift at the lowest temperature if the magnetic field is perpendicular to the CuO 2 plane, which points to a localization of spin in the 3 d ( x 2 − y 2 ) orbital. A simple model is presented based on the most fundamental findings. The analysis must have new consequences for theory of the cuprates.

127I NMR calculations in binary metal iodides by PBE-GGA, YS-PBE0 and mBJ exchange correlation potentials

We have calculated Nuclear Magnetic Resonance (NMR) spectroscopy for 127I (quadrupolar nuclei I=5/2) in binary metal iodides XI (X=Li, Na, K, Rb and Cs) by using PBE- GGA, YS- PBE0 and mBJ exchange correlation potentials. The results show that the nature of bonds between Iodine and metal atoms are ionic. The main contribution in NMR spectroscopy is related to the induced current inside the atomic sphere and the remainder of the unit cell volume contributes only a few ppm. Obtained NMR shifts are compared with the NMR shielding data and the NMR shielding for metal-p band varies across the series about 221ppm. Density of states results indicate that the largest contribution in the shielding comes from the I-core electrons (1s and 4d). The NMR shielding graphs show that there are negative linear correlation with slope −1.18, −1.16 and −1.01 by PBE- GGA, YS- PBE0 and mBJ, respectively. The computed results by mBJ are in good agreement with the experimental values.

Quadrupole shift of nuclear magnetic resonance of donors in silicon at low magnetic field

Shifts from the expected nuclear magnetic resonance frequencies of antimony and bismuth donors in silicon of greater than a megahertz are observed in electrically detected magnetic resonance spectra. Defects created by ion implantation of the donors are discussed as the source of effective electric field gradients generating these shifts via quadrupole interaction with the nuclear spins. The experimental results are modeled quantitatively by molecular orbital theory for a coupled pair consisting of a donor and a spin-dependent recombination readout center.

Pure shift 1 H NMR: what is next?

Currently, pure shift nuclear magnetic resonance (NMR) is an area of high interest. The aim of this contribution is to describe briefly how this technique has evolved, where it is now and what could be the next challenges in the amazing adventure of the development and application of pure shift NMR experiments. Copyright © 2016 John Wiley & Sons, Ltd.

Four-component relativistic density functional theory with the polarisable continuum model: application to EPR parameters and paramagnetic NMR shifts

ABSTRACTThe description of chemical phenomena in solution is as challenging as it is important for the accurate calculation of molecular properties. Here, we present the implementation of the polarisable continuum model (PCM) in the four-component Dirac–Kohn–Sham density functional theory framework, offering a cost-effective way to concurrently model solvent and relativistic effects. The implementation is based on the matrix representation of the Dirac–Coulomb Hamiltonian in the basis of restricted kinetically balanced Gaussian-type functions, exploiting a non-collinear Kramer's unrestricted formalism implemented in the program ReSpect, and the integral equation formalism of the PCM available through the stand-alone library PCMSolver. Calculations of electron paramagnetic resonance parameters (g-tensors and hyperfine coupling A-tensors), as well as of the temperature-dependent contribution to paramagnetic nuclear magnetic resonance (pNMR) shifts, are presented to validate the model and to demonstrate the importance of taking both relativistic and solvent effects into account for magnetic properties. As shown for selected Ru and Os complexes, the solvent shifts may amount to as much as 25% of the gas-phase values for g-tensor components and even more for pNMR shifts in some extreme cases.

Tight-binding theory of NMR shifts in topological insulatorsBi2Se3andBi2Te3

Motivated by recent nuclear magnetic resonance (NMR) experiments, we present a microscopic sp3 tight-binding model calculation of the NMR shifts in bulk Bi2Se3, and Bi2Te3. We compute the contact, dipolar, orbital and core polarization contributions to the carrier-density-dependent part of the NMR shifts in Bi209, Te125 and Se77. The spin-orbit coupling and the layered crystal structure result in a contact Knight shift with strong uniaxial anisotropy. Likewise, because of spin-orbit coupling, dipolar interactions make a significant contribution to the isotropic part of the NMR shift. The contact interaction dominates the isotropic Knight shift in Bi209 NMR, even though the electronic states at the Fermi level have a rather weak s-orbital character. In contrast, the contribution from the contact hyperfine interaction to the NMR shift of Se77 and Te125 is weak compared to the dipolar and orbital shifts therein. In all cases, the orbital shift is at least comparable to the contact and dipolar shifts, while the shift due to core polarization is subdominant (except for Te nuclei located at the inversion centers). By artificially varying the strength of spin-orbit coupling, we evaluate the evolution of the NMR shift across a band inversion but find no clear signature of the topological transition.

Electronic properties of GeTe and Ag- or Sb-substituted GeTe studied by low-temperatureTe125NMR

We have carried out $^{125}$Te nuclear magnetic resonance (NMR) in a wide temperature range of 1.5 -- 300 K to investigate electronic properties of Ge$_{50}$Te$_{50}$, Ag$_{2}$Ge$_{48}$Te$_{50}$ and Sb$_{2}$Ge$_{48}$Te$_{50}$ from a microscopic point of view. From the temperature dependence of NMR shift ($K$) and nuclear spin lattice relaxation rate (1/$T_1$), we found that two bands contribute to the physical properties of the materials. One band overlaps the Fermi level providing the metallic state where no strong electron correlations are revealed by Korringa analysis. The other band is separated from the Fermi level by an energy gap of $E_{\rm g}/k_{\rm B}$ $\sim$ 67 K, which gives rise to the semiconductor-like properties. First principle calculation revealed that the metallic band originates from the Ge vacancy while the semiconductor-like band may be related to the fine structure of the density of states near the Fermi level. Low temperature $^{125}$Te NMR data for the materials studied here clearly show that the Ag substitution increases hole concentration while Sb substitution decreases it.

Effective gyromagnetic ratios in a mixture of noble gases with artificial nuclear magnetization

The precession of nuclear magnetic moments for a noble gas in an external magnetic field upon the laser pumping of nuclear magnetization is considered. A shift of the nuclear magnetic resonance for a mixture of noble gases with different gyromagnetic ratios of nuclei is observed.

11B pulsed nuclear magnetic resonance study of DyNi2B2C single crystals

DyNi2B2C is the only compound in the RNi2B2C (R = rare-earth element) series where superconductivity at Tc ∼6.2 K coexists with the antiferromagnetic ordering below the Nèel temperature TN ∼10.3 K. This system is of great interest because superconductivity rarely coexists with magnetic ordering. 11B pulsed nuclear magnetic resonance (NMR) measurements were performed at 8.0056 T to investigate the local electronic structures and 4f spin dynamics of DyNi2B2C powders and single crystals. The spectrum for the single crystal showed three narrow resonance peaks at 295 K due to the nuclear Zeeman splitting of a nuclear spin I = 3/2 with quadrupolar perturbation. The 11B NMR Knight shift of the single crystal was very large and highly anisotropic at K = −0.60% and +0.27% for the fields parallel and perpendicular, respectively, to the c-axis at 295 K. Considering the anisotropy of the Knight shift, we were able to simulate the 11B NMR power pattern that agreed well with the measured spectrum. The linewidth for DyNi2B2C was also large and anisotropic, and the linewidth value increased rapidly at low temperatures. The 11B NMR shift and linewidth were found to be proportional to the magnetic susceptibility, indicating that the hyperfine field at the B site originates from the 4f spins of Dy. Above TN, the values for 1/T1 (the spin-lattice relaxation rate) and 1/T2 (the spin-spin relaxation rate) were very large, showing slight increases at low temperatures. Below TN, the values of 1/T1 and 1/T2 were suppressed significantly because of the slowing of the 4f spin fluctuation. This confirmed the huge change in Dy 4f spin dynamics across the antiferromagnetic transition.

Pseudo-Contact Shift in Periodic Paramagnetic Solids Via Density Functional Theory

Nuclear Magnetic Resonance (NMR) spectroscopy of paramagnetic solids represents an exceptional means for getting insight into structural and electronic properties of the systems, giving on the other hand a particularly involved response to analyse. Specifically, the overall isotropic shift is given by a combination of the Fermi contact term, dependent on the electronic structure of the paramagnetic site and on the strength and covalency of its bond with the observed centre, and on the pseudo-contact term, a relativistic dipolar contribution that gives information regarding the structure and the spatial arrangements of the sites in the system. In this work we present a protocol to extend the computation of the paramagnetic shielding in the presence of spin-orbit coupling towards solid systems, with which to calculate these two contributions explicitly via periodic solid-state Density Functional Theory (DFT) so to unravel detailed information hidden in the NMR spectrum. We describe how the involved properties such as g- and hyperfine tensors behave in paramagnetic solids where the spin-bearing ions are a major constituent of the crystal lattice. Finally it is clarified how to combine these quantities in order to separate the various terms contributing to the paramagnetic shielding, σs : this method enables to get deeper insight into the overall isotropic shift and shift anisotropy observed experimentally, and to identify information regarding electronic structure and geometry of the system. The method is applied to a series of solid-state LiTMPO4 (with TM=Mn, Fe, Co and Ni) powders and the corresponding 7Li and 31P NMR shifts are computed. From these results we outline differences in the extent of spin-orbit coupling effects and electron-nuclear magnetic interaction, and the various tensorial products are combined together to explicitly calculate all the terms involved in the description of σs . A detailed comparison is presented between contact and dipolar interactions within the same system and across the series, to untangle the dual nature of the overall isotropic shift and shift anisotropy.

Association of symmetrical alkane diols with pyridine: DFT/GIAO calculation of 1H NMR chemical shifts

Proton nuclear magnetic resonance (NMR) shifts of the free diol and of its 1 : 1 and 1 : 2 hydrogen-bonded complexes with pyridine have been computed for five symmetrical alkane diols on the basis of density functional theory, by applying the gauge-including atomic orbital method to geometry-optimized conformers. For certain conformers, intramolecular OH···OH interactions, evidenced by high NMR OH proton shifts, are further enhanced on going from the free diol to the corresponding 1 : 1 diol/pyridine complex. This is confirmed by atoms-in-molecules and non-covalent interaction plots. The computed OH and CH proton shifts for the diol and the two complexes correlate well with values obtained by analysing data from the NMR titration of the diols in benzene against pyridine. Shift values for the diols in neat pyridine are calculated by weighting the shifts of the various protons in the three forms (free diol, 1 : 1 and 1 : 2 diol/pyridine complexes) according to the experimentally determined association constants. The results are in good agreement with those observed, and after empirical scaling, the root mean square difference is 0.18 ppm. Copyright © 2016 John Wiley & Sons, Ltd.

NMR shift and relaxation measurements in pulsed high-field magnets up to 58 T

Nuclear magnetic resonance (NMR) experiments at fields up to 58T in pulsed magnets at the Dresden High Magnetic Field Laboratory are reported. The challenge to resolve NMR shifts in these time-dependent fields is addressed for the first time, and it is shown that this can indeed be accomplished with high precision with an internal reference. As a result, signal averaging is possible during a single magnetic field pulse, but also for multiple pulses. Thus, even very weak signals can in principle be recorded and their shifts can be determined. In a second set of experiments, the measurement of nuclear relaxation is investigated. Using adiabatic inversion with the inherent time dependence of the magnetic field and small-angle inspection, it is shown that relaxation measurements are possible, as well. The shift experiments were performed with 27Al NMR on a mixture of aluminum metal and a Linde type A zeolite. For the relaxation studies, 27Al NMR and 69Ga NMR on the metals aluminum and gallium were preformed, respectively.