Electric Quadrupole Coupling Constants Research Articles

Analysis and information content of quadrupolar NMR in glasses: 25Mg NMR in vitreous MgSiO3 and CaMgSi2O6

The static wideline and high-resolution magic angle spinning (MAS) 25Mg NMR lineshapes measured for isotopically enriched enstatite and diopside glasses indicate a wide distribution of the electric-field gradient (EFG) components at the 25Mg position caused by disorder. The correct characterization of this distribution requires simulations with special attention paid to the experimental parameters. Here, both the static spectra obtained by wideband excitation and the MAS-NMR spectra obtained via rotor-synchronized Hahn spin echo acquisition were successfully simulated with the Czjzek distribution model, using one consistent set of parameters. Average nuclear electric quadrupole coupling constants near 8 MHz and a distribution width around 4 MHz were obtained for both materials, which suggests that earlier results on these glasses need to be re-examined. The results of this study outline a general strategy for characterizing the local environments of strongly coupled quadrupolar nuclei in amorphous and glassy materials. Despite the discrepancies between the interaction parameters extracted from our data and those published in earlier NMR work, the best fit to the data indicate an average isotropic chemical shift near 13 ppm (vs. aqueous MgCl2 solution) for both the enstatite and diopside glasses. Assuming the applicability of the current database relating the 25Mg chemical shifts with coordination numbers in crystalline compounds, this value suggests that the Mg2+ ions are six-coordinated. This conclusion, however, is based on the simplifying assumption that the 25Mg spectrum comprises a Czjzek distribution centered at a single isotropic chemical shift value and stands in contrast to the results of recent isotope-selective neutron diffraction studies which give an average Mg-O coordination number of 4.4–4.5 for both glasses. However, reasonable fits to the MAS-NMR spectra can also be obtained when constraining the average isotropic chemical shift to 50 ppm, a value typical of four-coordinated Mg. We conclude that multiple Mg sites with different coordination numbers may well be present and that, in the present glasses, 25Mg NMR at typically used spinning rates and magnetic field strengths (20 kHz, 14.1 T) is not capable of resolving them due to excessive broadening by quadrupolar interactions.

A study of the conformational isomerism of n-propyl nitrate by microwave spectroscopy

The rotational spectrum of n-propyl nitrate was measured in the frequency range between 6 and 18 GHz using a Balle-Flygare Fourier transform microwave jet/cavity spectrometer. Parent, 13C and 15N isotopologue transitions for the lower-energy anti-gauche (AG) conformer were found using this instrument. The search for spectra from other conformers was performed using a broadband chirped-pulse jet spectrometer. Transitions from the anti-anti (AA) conformer were observed in this manner. Parent, 13C and 15N isotopologue transitions for the AA conformer were rescanned using the cavity instrument to improve resolution and the signal-to-noise ratio. Rotational, centrifugal distortion, and nuclear electric quadrupole coupling constants for all conformers/isotopologues were fit using Pickett’s SPFIT program. The structure of n-propyl nitrate is discussed considering these results.

Hyperfine structure of quadrupole rovibrational transitions in tritium-bearing hydrogen isotopologues

We perform a theoretical investigation of hyperfine interactions in the tritium-bearing isotopologues of the hydrogen molecule: HT, DT and T2. We report a set of hyperfine coupling constants: spin-rotation, spin-spin dipole and, in the case of the DT isotopologue, electric quadrupole coupling constants for all bound states of the three isotopologues in their ground electronic states. We determine positions and intensities of 656 217 hyperfine components of 38 971 quadrupole rovibrational transitions from the O, Q and S branches. The positions and intensities of the hyperfine components are necessary for a reliable interpretation of accurate measurements of rovibrational transition frequencies in tritium-bearing isotopologues of hydrogen, which are useful for tests of quantum electrodynamics for molecules and searches for new physics beyond the Standard Model.

Quasi-relativistic study of nuclear electric quadrupole coupling constants in chiral molecules containing heavy elements

A quasi-relativistic (two-component) zeroth-order regular approximation model potential approach is employed to calculate nuclear electric quadrupole coupling tensors of the chiral polyhalomethane derivatives CHBrClF and CHClFI. Each of these two chiral compounds contains two nuclei with electric quadrupole moments, which poses special challenges for an analysis of high-resolution rovibrational spectra and, thus, renders predictions of electric field gradients and resulting nuclear electric quadrupole coupling tensors in such molecules particularly valuable. The theoretical approach is studied with respect to the influence of relativistic effects, by comparison to scalar-relativistic and non-relativistic calculations, and electron correlation effects, which are included within different flavours of density functional theory. The quality of the calculations is assessed by comparison to results from experiments reported previously by Bauder et al. and Soulard et al., respectively. It is shown that the local density approximation exchange-correlation functional gives results that agree with experiment within 12 % for all nuclear quadrupole coupling tensor components of 79Br and 127I. This benchmark test of the quasi-relativistic approach indicates its applicability to support upcoming microwave experiments with chiral heavy-element containing main group compounds.

Hyperfine components of all rovibrational quadrupole transitions in the H2 and D2 molecules

We report results of a theoretical investigation of hyperfine interactions in two homonuclear isotopologues of the hydrogen molecule: H2 and D2. We present a set of hyperfine coupling constants: spin-rotation, spin-spin dipole and, in the case of the D2 molecule, electric quadrupole coupling constants for all bound states of the two isotopologues in their ground electronic X1Σg+state. We provide a list of positions and intensities of 220 997 hyperfine components of 16 079 rovibrational quadrupole transitions of the O, Q and S branches. The positions and intensities of the hyperfine components are necessary for a reliable interpretation of accurate measurements of rovibrational transition frequencies in H2 and D2, which are used for tests of the quantum electrodynamics of molecules and searches for new physics beyond the Standard Model.

Positions and intensities of hyperfine components of all rovibrational dipole lines in the HD molecule

We report results of a theoretical analysis of hyperfine interactions in the HD molecule. We present the calculated coupling constants: spin-rotation, spin-spin and electric quadrupole coupling constants for all bound states of HD in its ground electronic 1Σ state. We provide a list of positions and intensities of 108 320 hyperfine components of 5 129 dipole transitions from the P and R branches. The positions and intensities of the hyperfine components are necessary for a proper interpretation of accurate measurements of rovibrational transition frequencies in HD which are used for tests of quantum electrodynamics of molecules and searches for new physics beyond the Standard Model.

Spin-Polarized Hydrogen Depolarization Rates at High Hydrogen Halide Pressures: Hyperfine Depolarization via the HY-H Complex.

We measure the magnetization quantum beats of spin-polarized hydrogen (SPH) and spin-polarized deuterium (SPD) with a pickup coil, from the UV photodissociation of HCl, HBr, and DI, in the 5-5000 mbar pressure range. The pressure-dependent depolarization rate is linear at low pressures and reaches a plateau at higher pressures. The high-pressure depolarization rate is observed to be proportional to the halogen nuclear electric quadrupole coupling constant. We also investigate how the presence of an inert gas, SF6 or N2, affects the depolarization rate. The results are explained using a model in which depolarization occurs predominantly through an HY-H intermediate species (Y = Cl, Br, I).

Investigation of the two-color polarization spectroscopy between the excited states based on cesium atoms

Two-color polarization spectroscopy (TCPS) of cesium 6S<sub>1/2</sub>-6P<sub>3/2</sub>-8S<sub>1/2</sub> (852.3 nm + 794.6 nm) ladder-type system in a room-temperature vapor cell are investigated. The frequency of 852.3 nm laser used as a pump beam is locked on one of the hyperfine transitions between the ground state 6S<sub>1/2</sub> and excited state 6P<sub>3/2</sub> by the saturated absorption spectroscopy technique, which can populate some atoms on the 6P<sub>3/2</sub> excited state and induce anisotropy in the atomic medium. The frequency of 794.6 nm laser serving as a probe beam is scanned across the whole 6P<sub>3/2</sub>→8S<sub>1/2</sub> transition to ascertain this anisotropy, and thus the TCPS is obtained. In experiment, we measure and analyse the influence of frequency detuning of 852.3 nm pump laser on TCPS, and especially reveal that some of hyperfine energy levels of intermediate excited state 6P<sub>3/2</sub>, which has no direct interaction with the 852.3 nm pump laser, are also populated by a small fraction of atoms with a specific speed in the direction of pump laser beam due to Doppler effect, so they also have contribution to the TCPS when the 794.6 nm probe laser is scanned to the resonance transition line between the 6P<sub>3/2</sub> and 8S<sub>1/2</sub> states after the Doppler frequency shift has been considered. In addition, we prove that the atomic coherence like electromagnetically induced transparency effect obviously results in a narrower line width of TCPS in the case of counter-propagating experimental configuration than that in the case of pump beam co-propagating with the probe beam in the Cs vapor cell. Finally, we apply the TCPS with dispersive shaped feature to frequency stabilization with no modulation, and the frequency fluctuations of 794.6 nm laser are ～0.5 MHz and ～9.2 MHz for the frequency-locking and free running in ～225 s, respectively. The above research work is expected to play a role in precisely measuring the atomic energy level structure and its related hyperfine structure constant (magnetic dipole and electric quadrupole coupling constants), and also in stabilizing the laser frequency to the excited state transition especially for the optical fiber communication, two-color laser cooling/trapping neutral atoms, optical filter, etc.

Fourier Transform Microwave Spectra of the Nitrogen Molecule-Ethylene Sulfide and Nitrogen Molecule-Dimethyl Sulfide Complexes.

We recorded the rotational spectra of N2-ethylene sulfide (ES) and N2-dimethyl sulfide (DMS) including the 15N2 and 15N14N isotopomers in the frequency range of 5-25 GHz by using a Fourier transform microwave spectrometer. The b-type transitions for the ortho and para states of 14N2-ES and 15N2-ES and c-type transitions of 14N2-DMS and 15N2-DMS were observed. The 15N14N-ES and 15N14N-DMS species were found to exist in two isomeric forms: inner (14N15N-ES and 14N15N-DMS) and outer (15N14N-ES and 15N14N-DMS). Neither the -ES nor -DMS complexes showed weak accompanying spectra, which had been observed for N2-ethylene oxide (EO). This is because the potential barriers to internal rotation of ES and DMS are higher than that of EO. The spectra were analyzed by an A-reduced asymmetric-top rotational program with less than 4 kHz standard deviation, except for the 15N14N-DMS and 14N15N-DMS complexes. Rotational, centrifugal distortion, and nuclear electric quadrupole coupling constants were determined by the spectral analysis. The V3 potential barrier to internal rotation of the two equivalent methyl groups of DMS in the ortho and para states of the 15N2-DMS complex was determined to be about 740 cm-1. We performed ab initio calculations in order to complement the information on the intracomplex motions obtained from the experimental spectra.

Characterization of the [18.28]0--a3Δ1 (0,0) band of tantalum nitride, TaN.

The [18.28]0--a3Δ1 (0,0) band near 647 nm of tantalum nitride, TaN, has been recorded and analyzed field-free and in the presence of static electric and magnetic fields. The fine and hyperfine parameters for the a3Δ1 and [18.28]0- states are determined. The 181Ta(I = 7/2) axial nuclear electric quadrupole coupling constant, eQq0, and the effective magnetic hyperfine coupling constant, h1, are used to garner insight into the nature of electronic states. The Stark tuning of the P(2) and Q(1) lines was analyzed to determine the molecular frame permanent electric dipole moment, μ→el, for the a3Δ1 state of 4.49 ± 0.09 D. The Zeeman effect on the P(1) line was analyzed to determine an upper limit of the magnetic moment, μ→m, for the a3Δ1 state. Scalar-relativistic coupled-cluster calculations for eQq0 and μ→el of the a3Δ1 state are also reported and compared with experimental results. The determined properties are compared with the predicted values and the implication of the proposed scheme for determination of the 181Ta magnetic quadrupole moment is discussed.

Hyperfine structure measurements of neutral iodine atom (127I) using Fourier Transform Spectrometry

We report the hyperfine Structure (hfs) splitting observations of neutral iodine atom (II) in the 6000 – 10,000 cm−1 near infrared spectral region. The measurements were carried out using a high-resolution Fourier Transform Spectrometer (FTS), where an electrodeless discharge lamp (EDL), excited using microwaves, was employed as the light source and InGaAs as the light detector. A specially designed setup was used to lower the plasma temperature of the medium so as to reduce the Doppler width and consequently to increase the spectral resolution of hfs components. A total of 183 lines with hfs splitting have been observed, out of which hfs in 53 spectral lines are reported for the first time. On the basis of hfs analysis, we derived the magnetic dipole and electric quadrupole coupling constants, A and B respectively for 30 even and 30 odd energy levels and are compared with the values available in the literature. New hfs values for 5 even and 4 odd levels are also reported here for the first time.

Hyperfine field, electric field gradient, quadrupole coupling constant and magnetic properties of challenging actinide digallide

In this paper, we explore the structural and magnetic properties as well as electric field gradient (EFG), hyperfine field (HFF) and quadrupole coupling constant in actinide digallide AcGa2 (Ac = U, Np, Pu) using LDA, GGA, LDA+U, GGA+U and hybrid functional with Wu-Cohen Generalized Gradient approximation HF-WC. Relativistic effects of the electrons are considered by including spin-orbit coupling. The comparison of the calculated structural parameters and magnetic properties with the available experimental results confirms the consistency and hence effectiveness of our theoretical tools. The calculated magnetic moments demonstrate that UGa2 and NpGa2 are ferromagnetic while PuGa2 is antiferromagnetic in nature. The EFG of AcGa2 is reported for the first time. The HFF, EFG and quadrupole coupling constant in AcGa2 (Ac = U, Np, Pu) are mainly originated from f-f and p-p contributions of Ac atom and p-p contribution of Ga atom.

Characterization of the [18.42]0+ – X1Σ+ (0, 0) band of tantalum nitride, TaN

High resolution laser-induced fluorescence (LIF) spectra of the [18.42]0+ − X1Σ+ (0,0) band of tantalum nitride, TaN, near 543nm, have been recorded and analyzed field-free and in the presence of a static electric field. The nuclear electric quadrupole hyperfine structure due to 181Ta(I=7/2) was resolved and analysis of the field-free spectrum yielded nuclear electric quadrupole coupling constants, eQq0, of −0.24025(75)cm−1 and −0.05755(76)cm−1 for the X1Σ+ and [18.42]0+ states, respectively. The Stark tuning of the R(0) and P(1) lines was analyzed to determine the magnitude of the molecular frame electric dipole moments, |μ→el|, of 3.33(4)D and 4.48(3)D for the X1Σ+ and [18.42]0+ states, respectively. The |μ→el| and eQq0 values are discussed in terms of predicted molecular orbitals for the X1Σ+ and [18.42]0+ states.

Accurate determination of the nuclear quadrupole moment of xenon from the molecular method

This study provides a new determination of the nuclear electric quadrupole moment (NQM) for 131Xe, which is achieved by the molecular method. Dirac-Coulomb Coupled Cluster calculations with a Gaunt correction (DC+G-CC) of electric field gradients (EFGs) and experimental nuclear quadrupole coupling constants of six molecular systems (XeH+, XeCuF, XeCuCl, XeAgF, XeAgCl and XeAuF) were considered. The best NQM obtained by our DC+G-CCSD-T EFGs was −114.6(1.1) mbarn, which is recommended as the new reference value for this nuclide given the high level electron structure calculations done here.

Electric quadrupole interaction in cubic BCC α-Fe

Mössbauer transmission spectra for the 14.41-keV resonant line in 57Fe have been collected at room temperature by using 57Co(Rh) commercial source and α-Fe strain-free single crystal as an absorber. The absorber was magnetized to saturation in the absorber plane perpendicular to the γ-ray beam axis applying small external magnetic field. Spectra were collected for various orientations of the magnetizing field, the latter lying close to the [110] crystal plane. A positive electric quadrupole coupling constant was found practically independent on the field orientation. One obtains the following value Vzz = +1.61(4) × 1019 Vm−2 for the (average) principal component of the electric field gradient (EFG) tensor under assumption that the EFG tensor is axially symmetric and the principal axis is aligned with the magnetic hyperfine field acting on the 57Fe nucleus. The nuclear spectroscopic electric quadrupole moment for the first excited state of the 57Fe nucleus was adopted as +0.17 b. Similar measurement was performed at room temperature using as-rolled polycrystalline α-Fe foil of high purity in the zero external field. Corresponding value for the principal component of the EFG was found as Vzz = +1.92(4) × 1019 Vm−2. Hence, it seems that the origin of the EFG is primarily due to the local (atomic) electronic wave function distortion caused by the spin–orbit interaction between effective electronic spin S and incompletely quenched electronic angular momentum L. It seems as well that the lowest order term proportional to the product L·λ·S dominates, as no direction dependence of the EFG principal component is seen. The lowest order term is isotropic for a cubic symmetry as one has λ=λ 1 for cubic systems with the symbol 1 denoting unit operator and λ being the coupling parameter.

Magnetic anisotropy in FeSb studied by 57Fe Mössbauer spectroscopy

The Fe1+xSb compound has been synthesized close to stoichiometry with x=0.023(8). The compound was investigated by 57Fe Mössbauer spectroscopy in the temperature range 4.2–300K. The antiferromagnetic ordering temperature was found as 232K i.e. much higher than for the less stoichiometric material. Regular iron was found to occupy two different positions in proportion 2:1. They differ by the electric quadrupole coupling constants and both of them exhibit extremely anisotropic electric field gradient tensor (EFG) with the asymmetry parameter η≈1. The negative component of both EFGs is aligned with the c-axis of the hexagonal unit cell, while the positive component is aligned with the 〈120〉 direction. Hence, a model describing deviation from the NiAs P63/mmc symmetry group within Fe-planes has been proposed. Spectra in the magnetically ordered state could be explained by introduction of the incommensurate spin spirals propagating through the iron atoms in the direction of the c-axis with a complex pattern of the hyperfine magnetic fields distributed within a–b plane. Hyperfine magnetic field pattern of spirals due to major regular iron is smoothed by the spin polarized itinerant electrons, while the minor regular iron exhibits hyperfine field pattern characteristic of the highly covalent bonds to the adjacent antimony atoms. The excess interstitial iron orders magnetically at the same temperature as the regular iron, and magnetic moments of these atoms are likely to form two-dimensional spin glass with moments lying in the a–b plane. The upturn of the hyperfine field for minor regular iron and interstitial iron is observed below 80K. Magneto-elastic effects are smaller than for FeAs, however the recoilless fraction increases significantly upon transition to the magnetically ordered state.

DFT investigation of the electronic structure of amphetamines: effect of substituent on O and N chemical shielding and electric field gradient tensors

To understand the relationship between the electronic structure of amphetamines and their biological activity, a computational investigation was carried out to characterise the 17O and 14N, electric field gradient (EFG) tensors and nuclear quadrupole coupling constants (NQCC) as well as 17O, 15N, 13C and 1H chemical shielding tensors of amphetamines. Calculation were performed with the B3LYP and PW91P86 density functional theory (DFT) methods with the 6-311++G(d,p) basis set. The anisotropic (Δσ) and isotropic (σiso) shielding are in good agreement with the available experimental data. The results indicate that the EFG and σ at oxygen are insensitive to substitution at the N and C10 positions in amphetamines. In contrast, the nitrogen EFG and σ are quite sensitive towards substituent changes. Furthermore, it was found that EFG tensors are more sensitive than σ tensor to the electron density distribution in amphetamines. Biological activities of amphetamines were found to depend upon the electron density distribution in the region of N atoms.

Quantum beat spectroscopy: Stimulated emission probe of hyperfine quantum beats in the atomic Cs8p2P3/2level

Measurements of hyperfine polarization quantum beats are used determine the magnetic dipole (A) and electric quadrupole (B) coupling constants in the excited atomic Cs 8p level. The experimental approach is a novel combination of pulsed optical pumping and time-delayed stimulated emission probing of the excited level. From the measured evolution of the atomic linear polarization degree as a function of probe delay time, we determine the hyperfine coupling constants A = 7.42(6) MHz and B = 0.14(29) MHz.

The germanides ScTGe (T = Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au) – Structure and 45Sc solid state NMR spectroscopy

The germanides ScTGe (T = Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, Au) were obtained in X-ray pure form by arc-melting of the elements. The structures of the members with T = Co, Ni, Cu, Rh, Pd, Ag, Ir, and Pt were refined on the basis of single crystal X-ray diffractometer data. The germanides with T = Cu, Ru, Pd, Ag crystallize with the hexagonal ZrNiAl type structure, space group P6¯2m and those with T = Co, Ni, Rh, Ir, Pt adopt the orthorhombic TiNiSi type. ScAuGe is isotypic with NdPtSb. All germanides exhibit single scandium sites. A simple systematization of the structure type according to the valence electron concentration is not possible. The 45Sc solid state NMR parameters (Knight shifts and nuclear electric quadrupole coupling constants) of those members crystallizing in the TiNiSi structure show systematic trends as a function of valence electron concentration number. Furthermore, within each T-group the Knight shift decreases with increasing atomic number; this correlation also includes previously published results on the isotypic silicide family. The 45Sc quadrupolar interaction tensor components are generally well-reproduced by quantum mechanical electric field gradient calculations using the WIEN2k code.

H₂-AgCl: a spectroscopic study of a dihydrogen complex.

H2-AgCl has been observed on a Fourier transform microwave spectrometer equipped with laser ablation source and determined to be a dihydrogen complex. Transitions up to J = 3-2 have been measured and analyzed for four isotopologues of the complex containing ortho and para H2. The ortho and para spin states have been included in one fit, a deviation from the typical H2 complex. Rotational constants B and C, centrifugal distortion constants Δ(J) and Δ(JK), nuclear electric quadrupole coupling constants χ(aa), χ(bb), and χ(cc) for (35)Cl and (37)Cl have been fit for both spin states while nuclear spin-nuclear spin constants D(aa), D(bb), and D(cc), and nuclear spin-rotation constant C(aa) have been reported for the ortho spin state. Quantum chemical calculations predict a strong bonding interaction and the strength of the complex has been related to reported χ(aa) and Δ(J) values amongst a host of comparable species, including the AgCl monomer itself. Bond lengths have been determined for Ag-Cl, Ag-H2 center-of-mass, and H-H and are reported.