Microwave spectra of eight isotopic modifications of 1-chloro-1-fluoroethylene

The rotational spectra of eight isotopomers of 1-chloro-1-fluoroethylene in the 6-22 GHz region have been collected and analyzed. Each rotational transition is split into hyperfine components by the chlorine (either ³⁵Cl or ³⁷Cl) nuclear quadrupole coupling interaction and additionally, one or more smaller interactions such as the spin-rotation interaction due to the fluorine atom, hydrogen-hydrogen spin-spin coupling interactions, and in appropriately substituted species, the deuterium nuclear quadrupole hyperfine interaction. The rotational constants derived from these isotopomers allow the determination of average and Kraitchman substitution structures for 1-chloro-1-fluoroethylene, whereas the availability of the diagonal chlorine nuclear quadrupole coupling constants for all the isotopomers provides complete quadrupole coupling tensors for both ³⁵Cl and ³⁷Cl. In the course of this work, the rotational spectrum of an excited vibrational state of the normal isotopomer was observed, which ab initio calculations suggest should be assigned to ν₉=1, an in-plane bending motion at the CFCl end of the molecule.     

Electronic structure and indirect spin-spin interactions in bournonite (CuPbSbS3) according to antimony nuclear quadrupole resonance

A complex sulfide CuPbSbS₃ (bournonite) has been studied by the nuclear quadrupole resonance on ^121,123Sb. The temperature dependences of the spectroscopic and relaxation parameters in the temperature range of 10–295 K have been obtained. The crystallochemical features of the environment of the two non-equivalent Sb positions in the unit cell have been revealed from the nuclear quadrupole resonance spectra. The existence of the lattice vibrations with the frequency ω = 110 cm^?1 has been demonstrated on the basis of the temperature dependence of the nuclear quadrupole resonance frequencies. Slow beats have been observed on the decay curve of the spin echo signal. Experimental data have been analyzed in order to reveal the existence of the indirect spin-spin interactions involving Sb atoms. The indirect spin-spin coupling constant has been estimated as J = 2.5 ± 0.5 kHz.     

Hyperfine spectrum of NaF

The molecular beam electric resonance technique has been used to conduct a high precision examination of the hyperfine spectrum of ²³Na¹⁹F. Coupling constants for the nuclear electric quadrupole interactions, the spin-rotation interactions, the tensor and scalar spin-spin interactions, and their dependence on vibrational and rotational state have been determined.     

161Dy Mössbauer measurements in DyBa2Cu3O7−x

Superconducting and non-superconducting samples of DyBa₂Cu₃O_7?x have been examined by Mössbauer spectroscopy down to 0.05 K. The saturated Dy³⁺ sublattice 4f shell magnetic moments and quadrupole interactions show fairly wide distributions in both samples. These are attributed to crystal field inhomogeneities. Neither the Dy³⁺ paramagnetic relaxation rates nor the isomer shifts show any evidence of coupling between Dy³⁺ and a possible conduction band.     

Influence of Si on spin and charge density changes in bcc-iron

The influence of Si on the ⁵⁷Fe and ¹¹⁹Sn site hyperfine (hf) fields and isomer shifts has been studied for a series of Fe-Si alloys containing up to ca. 13 at% Si and ca. 0.9 at% ¹¹⁹Sn. The observed changes of the hf fields and the isomer shifts have been interpreted as reflecting spin and charge density changes, respectively. The following correlations could be established: hf field H(0,0) vs. isomer shift IS(0,0) of undisturbed atomic neighbour configurations (0,0), average hf field, H? vs. average isomer shift, $\text{IS}$; average hf field, H? vs. average number of Si atoms within the first two neighbour shells, N?. Based on the f correlations the following hf coupling constants have been determined: a) the hf coupling constant for s-like itinerant electrons are 690 kOe/s-el for Fe and 2100 kOe/s-el for Sn, b) the average hf coupling constants are 660 kOe/s-el and 2100 kOe/s-el for Fe and Sn, respectively. From the correlation between H? and N? the changes in the spin or charge densities caused be one Si atom per unit cell, η, have been deduced as follows: η(Fe)=0.17 and η(Sn)=0.03. Comparison is made with previously reported equivalent results for the Fe-Al system.     

Nuclear hyperfine coupling interactions in the rotational spectra of the linear and bent isomers of HF-N2O

The rotational spectra of six isotopomers of the linear and bent isomers of HF-N₂O have been collected in the 7-18 GHz region with a Fourier transform microwave spectrometer. The nuclear hyperfine structure in the spectra produced by HF spin-spin coupling interaction and nuclear quadrupole coupling interactions due to the D nucleus of DF and the nuclei of N₂O have been resolved and analyzed. In the linear isomer, H in HF is bonded to the terminal N in N₂O. The NF bond lengths are 2.9808(2) Å for the HF-containing isotopomers and 2.9732(2) Å for the DF-containing isotopomers. The zero point angles are 23.1° for HF and 31-34° for N₂O. The hyperfine constants suggest that the HF bond is lengthened by 0.0105 Å upon complexation and that the electric field gradients of the two nitrogen nuclei in N₂O are perturbed differently in the complex. In the bent isomer, the hydrogen bond is formed between HF and O in N₂O. The intermolecular distances are 3.4942(2) Å for the HF-containing isotopomers and 3.4436(2) Å for the DF-containing isotopomers, with HF and N₂O forming angles of 34° and 46°, respectively, with the intermolecular axis. The nuclear quadrupole coupling constants of the two nitrogen nuclei do not indicate electric field gradient perturbation in this isomer.     

Cluster calculation of electronic structure and hyperfine interactions for α-Fe2O3

The MSX_α cluster technique has been used to study the electronic structure of hematite α-Fe₂O₃, where iron is formally in a 3d₅⁶S state. The calculated energy levels are compared with X-ray emission and photoelectron spectra. The wave functions have been used to compute the charge distribution, as well as hyperfine parameters such as quadrupole coupling constant, isomer shift and magnetic hyperfine field. The results indicate a considerable influence of chemical bonding on these parameters due to charge transfer and covalency. From the calculated field gradient and the measured quadrupole coupling constant a nuclear quadrupole moment for ^57mTe of about 0.11b is deduced. This value is smaller than the most recent estimates of 0.15b based on the ionic model but not as small as the value of 0.082b obtained from first principles calculations on iron dihalides.     

Microwave spectrum of NF2

About 350 lines in the microwave spectrum of NF₂ have been measured in various ranges of frequency between 13.0 and 65.2 GHz by using two types of Zeeman effect spectrometers. Complete assignment of all lines has been achieved and, via the general microwave computer program SPINRO, the rotational constants, centrifugal distortion constants, dipole moment, electronic spin-rotation coupling constants, the constants for the coupling of the several nuclear spins with the electron spin and the nitrogen quadrupole coupling constants have all been obtained.By drawing upon the observed vibrational frequencies the average geometry of NF₂ has been evaluated. Force constants and Coriolis coupling constants have also been derived.The values of the spin coupling constants for N and for F indicate that NF₂ is a π-radical with the spin density mainly located on nitrogen. The multiplet patterns indicate that the ground electronic state wavefunction is antisymmetric to rotation about the molecular symmetry axis and so, for a π-radical, identifies the ground state as ²B₁ as has previously been assumed for this molecule.     

Density-functional theory calculation of the nuclear magnetic resonance indirect nuclear spin—spin coupling constants in C60

Density-functional theory is used to study the nuclear magnetic resonance (NMR) indirect nuclear spin-spin coupling constants in C₆₀. Knowledge of these coupling constants may help in the analysis of future experimental NMR studies of ¹³C-enriched C₆₀. At the Becke 3-parameter Lee-Yang-Parr (B3LYP) Kohn-Sham level, the one-bond couplings within pentagons and between pentagons are 62 Hz and 77 Hz, respectively; the corresponding geminal couplings are 7 Hz and 1 Hz, respectively. Except for the vicinal couplings (about 4 Hz), the long-range couplings are all 1 Hz or smaller. This is the largest theoretical calculation to date of the complete set of indirect nuclear spin-spin coupling constants of a molecular system; it has been made possible by solving the response equations only for the perturbing operators related to one nuclear magnetic moment, making the calculation feasible.     

The state of 57Fe in pure and oxidized tin chalcogenides by Mössbauer spectroscopy

A Mössbauer spectroscopy study has been made of the stabilization states of ⁵⁷Fe in pure tin chalcogenides. The values of the isomer shifts and the quadrupole splittings lead to the conclusion that iron presents the electronic configuration 3d⁵4s^x at high spin in the interstitial position. This result is confirmed varying the ⁵⁷Fe neighbours by partial substitution of tellurium with oxygen. In this case, too, the values of Mössbauer parameters confirm the same results. The quadrupole moment present in pure SnTe doped ⁵⁷Co, and the shift of isomer shift towards less positive values for the oxidizated samples have been qualitatively justified as well.     

Resonance spectroscopy of γ-radiation on Au (I) and Au (III) compounds

Isomer shift (IS) and electric quadrupole splitting (QS) of the 77 keV γ-rays of Au¹⁹⁷ were investigated for a large number of Au (I) and Au (III) compounds at 4.2 °K by nuclear γ-resonance Spectroscopy. A close correlation between the observed isomer shifts and the spectrochemical series of the ligands was observed. For each oxidation state, isomer shift and electric quadrupole splitting show approximately a linear relationship. On the basis of LCAO-MO theory, the experimental results are interpreted by covalency effects in the molecular orbitals, synergic coupling of σ- and π-bonds, and the empirically known donor and acceptor properties of the ligands.     

The high resolution rotational spectrum of 2-cyanoaziridine

The microwave spectrum of 2-cyanoaziridine has been measured and assigned. Only the spectrum of the cis isomer has been detected although extensive searches for transitions from the trans isomer have been made, suggesting that it is at least 11 kJ mol^?1 less stable. The following nuclear quadrupole coupling constants were obtained: χ_aa(1) = ?1.249(14), χ_bb(1) = 1.407(12), χ_aa(2) = ?3.547(6), χ_bb(2) = 1.865(8) MHz, the former pair probably referring to the amino nitrogen and the latter pair to the nitrile nitrogen. The rotational constants derived from the analysis are: A = 16877.718(32), B = 3528.931(4), C = 3373.065(4) MHz, D_N = 1.10(4) kHz.     

Messung der rückstoßfreien Resonanz-Absorption am 6,2 keV-Niveau in181Ta

A strong recoilless resonance absorption was observed for the extraordinarily narrow 6.2 keV level (T _1/2=6.8 μs) of¹⁸¹Ta. Using sources of¹⁸¹W in W-metal and Ta-metal absorbers, a linewidth of about 9 times the natural width was obtained, with an enormous isomer shift of +(0.85±0.02) mm/sec, which is equivalent to a shift by 260 times the natural linewidth. Recoilless resonance spectra of cold worked and of oxygen doped absorbers showed a high sensitivity of the linewidth against lattice imperfections due to inhomogeneous quadrupole interactions and isomer shifts. Measurements of the residual resistivity ratio and of the lattice constant of the impurity doped absorbers yielded a linear correlation between linewidth and isomer shift.     

Electronic and structural properties of some ternary neptunium (VII) oxides from 237Np Mössbauer spectroscopy

The 60 kev Mössbauer resonance of ²³⁷Np has been measured in some complex oxides of heptavalent neptunium. The nature of bonding and the molecular symmetry are discussed on the basis of the isomer shift and quadrupole coupling constant data. The molecular character of the compounds is evidenced by the low Debye temperatures and the strong bond covalency. The quadrupole coupling constant is temperature independent; this reveals the absence of any non-bonding states of ? electrons.     

Hartree-Fock cluster investigations of electronic structure and nuclear quadrupole interaction in the superionic conductor Li3N

The nuclear quadrupole interactions for⁷Li and¹⁴N nuclei are studied for lithium nitride crystal using the Hartree-Fock cluster procedure to obtain the electronic structure. The influence of the Madelung potential due to the ions outside the cluster was incorporated in a first-principle manner. Our results for the quadrupole coupling constants will be compared with experimental data and the results of a recent band calculation.     

Magnetic and Mössbauer spectral studies of nano crystalline cobalt substituted magnesium ferrites (MgxCo1 − xFe2O4)

The electronic structure of the heme unit of deoxyhemoglobin including the proximal imidazole has been studied using the first-principles Hartree-Fock procedure. Our results for the ^57mFe isomer shift and asymmetry parameter are in very good agreement with the values obtained from Mössbauer spectroscopy measurements. The ^57mFe nuclear quadrupole coupling constant is smaller than the experimental result and possible ways to improve the agreement in the future are discussed. Improved analysis of the Mössbauer data, removing some approximations made for deriving the magnetic hyperfine tensor for the ^57mFe nucleus, is suggested to allow quantitative comparison with our results in the future.     

Nuclear quadrupole coupling interactions in the rotational spectrum of tryptamine

Four conformers of tryptamine have been detected in a supersonic expansion and characterized by laser ablation molecular beam Fourier transform microwave spectroscopy LA-MB-FTMW in the 5–10 GHz frequency range. The quadrupole hyperfine structure originated by two ¹⁴N nuclei has been completely resolved for all conformers and used for their unambiguous identification. Nuclear quadrupole coupling constants of the nitrogen atom of the side chain have been used to determine the orientation of the amino group involved in N–H?π interactions: to the π electronic system of the pyrrole unit in the Gauche-Pyrrole conformers (GPy) or to the phenyl unit in the Gauche-Phenyl ones.     

Mossbauer study of the Cu-Cd ferrite system

The magnetic properties of the Cd_xCu_1?xFe₂O₄ ferrite system (x = 0 to 1) have been investigated by means of Mossbauer Spectroscopy. Mossbauer Spectra for x = 0.0 to 0.6 suggest the existence of two hyperfine fields, one due to the Fe³⁺ tetrahedral ions (A-sites) and the other due to Fe³⁺ octahedral ions (B-sites), while for x = 0.7 it shows relaxation behaviour and for x ? 0.8 it exhibits a paramagnetic quadrupole doublet. The systematic dependence of the isomer shift, quadrupole interactions and nuclear fields of ⁵⁷Fe³⁺ ions in both A- and B-sites has been determined as a function of cadmium content. The variation of nuclear magnetic fields at the A- and B-sites are explained on the basis of A-B and B-B supertransferred hyperfine interactions. Analysis of the relaxation spectrum observed at x = 0.7 (300 K) suggests that the relaxation mechanism is due to domain wall oscillations. It has been found here that the QS increases from CuFe₂O₄ as the cadmium concentration is increased.     

High-resolution spectroscopy near the continuum limit: the microwave spectrum of trans-3-bromo-1,1,1,2,2-pentafluoropropane

ABSTRACT

The microwave spectrum of 3-bromo-1,1,1,2,2-pentafluoropropane has been observed using CP-FTMW spectroscopy. Potential energy scans have been performed and confirm the existence of two conformers – trans and gauche – for which further structural optimisations and electric field gradient calculations have been performed in order to get highly accurate nuclear quadrupole coupling constants for assignment purposes. The combination of multiple conformers and large nuclear quadrupole coupling constants produce a very dense spectrum at an estimated 1?transition/MHz, near the continuum limit. This spectral density makes it necessary to have very sophisticated computational approaches in order to get geometric and electronic structures that are very close to experimental observation. Analysis of the spectrum allowed for the assignment of the trans conformer, but the gauche proved to be prohibitive, although it is believed to be present in the current spectrum. Full analysis of the rotational spectroscopic parameters of two isotopologues – the⁷⁹Br and⁸¹Br – have been observed and are reported. Geometric analysis of the experimentally observed conformer is also reported using Kraitchman coordinate and second moments arguments. Further analysis of the spectrum reveals the occurrence of dipole-forbidden, nuclear quadrupole allowed transitions with one forbidden transition possessing the first known x-type forbidden transition linkage pathway.     

The129I hyperfine interaction in fatty acids studied by Mössbauer spectroscopy

Oleic acid substituted by iodine and saponified by Ca²⁺ cations has been studied by¹²⁹I Mössbauer spectroscopy. The quadrupole coupling constants and isomer shifts, determined from the γ-resonance spectra recorded at 4.2 K, have been described by 5p and 5s orbital populations of iodine. It was also found that saponification of the fatty acid has no significant influence on the measured iodine bonds. However, the increased order of fatty acids in soap form is reflected by narrowing of the resonant linewidth due to the reduction of the electric field gradient distribution.