Magnetic shielding studies on the alkali molecules Na2 and Cs2 by NMR

NMR in the alkali molecules Na₂ and Cs₂ is performed by the atom-molecule exchange optical pumping method. The shielding differences σ(Na)?σ(Na₂)=(29±16)·10^?6 and σ(Cs)?σ(Cs₂)=(221±12)·10^?6 are obtained. The investigation of the contribution of the valence electron to the magnetic shielding is supported by a NMR experiment in free Cs⁺ ions, which yields the shielding difference σ(Cs)?σ(Cs⁺)=(14±12)·10^?6. These measurements allow an estimation of the spin rotation interaction constant in these molecules.     

Magnetic shielding and spin-rotation interaction in ground state alkali molecules

Precision measurements of nuclear magnetic dipole moments in alkali molecules are performed using atom-molecule exchange optical pumping. A comparison with measurements on alkali atoms gives the magnetic shielding differences between atoms and molecules and an approximate value for the spin-rotation interaction constant of the alkali molecules. It is reported on experiments on³⁹K₂ and⁸⁷Rb₂.     

A hydrocarbon trinegative ion

Experimental values for ¹H and ¹⁹F nuclear shielding anisotropies obtained from solid state, nematic phase, and molecular beam measurements are reviewed. Certain discrepancies are pointed out. An anisotropy operator is defined as a sum of two operators corresponding to the Lamb and high frequency terms. Approximations to the high frequency operator are given. Scales of absolute shielding constants are obtained, so that the magnitudes of the anisotropies can be discussed on the basis of non-empirical and semi-empirical calculations, and of the experimental results. The hypothesis due to Ramsey that the potential is constant for a given nucleus in different molecules is used to obtain approximate values for the Lamb term in the nuclear shielding constant.

The distinction between shielding in large and small molecules is stressed. For the fluoromethanes and fluorobenzene the results of CNDO/2 molecular orbital calculations are used for a qualitative discussion of the anisotropies.     

129Xe diffusion in a ferroelectric liquid crystal

Measurements of ¹²⁹Xe self-diffusion and shielding as a function of temperature were performed to cover the different phases of the ferroelectric liquid crystal FELIX-R&;D. The shielding data prove untwisting of the helical structure in the nematic phase (i.e. non-chiral nematic phase) of FELIX-R&;D. Self-diffusion measurements were carried out in a direction parallel to the main magnetic field of the NMR spectrometer. However, in order to yield the anisotropy of the xenon self-diffusion tensor a few measurements also were performed in the perpendicular direction. A special technique, based on the observation of the second spin echo instead of the conventional first one, was applied to avoid convection problems. The experiments reveal all the phase transitions and a continuous decrease in the self-diffusion constant along the external magnetic field, D‖, when moving from the isotropic to the smectic C? phase. The respective activation energy E‖ appears to vary remarkably, however, being about the same in the isotropic and smectic C? phases. In the smectic mesophases significantly faster xenon self-diffusion was detected in the perpendicular direction than in the parallel direction. The detected self-diffusion constant D ⊥ in the perpendicular direction seems to remain almost constant in the smectic mesophases and close to the value of the self-diffusion constant in the isotropic phase. The results are in agreement with the structural features of smectic phases and indicate redistribution of xenon atoms towards the interlayer space of smectic mesophases.     

A full configuration interaction calculation of the density dependence of the 3He shielding constant

The interaction-induced changes in the ³He shielding constant of the helium dimer have been calculated using the full configuration interaction method and large basis sets. From these data the first virial coefficient for the ³He isotropic shielding constant in gaseous helium has been determined. At room temperature it is negligibly small, approximately ?0.006 cm³ mol^?1 and it increases monotonically with temperature. This behaviour is caused by the monotonic dependence of the isotropic shielding constant of He₂ on the interatomic distance. In addition. the non-relativistic value of the shielding constant of the isolated He atom was estimated to be σ^iso = 59.932 ppm.     

Nuclear magnetic shielding tensors of207Pb2+ in Pb(NO3)2

The NMR signals of²⁰⁷Pb were observed in a single crystal of Pb(NO₃)₂ and could be assigned to the four different Pb²⁺ sites by the dependence of the linewidths on the orientation. Four different nuclear magnetic shielding tensors with equal principal values but with different characteristic vectors could be determined. The symmetry of the shielding tensors is in agreement with the symmetry at the Pb²⁺ sites. It is shown, that intermolecular contributions can not account for the anisotropy of the nuclear magnetic shielding, which is 3 of the isotropic absolute magnetic shielding.     

Helmet-size vessels of high-Tc oxide superconductor for magnetic shield

We have developed a very large magnetic shielding vessel made from high-T_c Bi-Pb-Sr-Ca-Cu-O superconductor and have experimentally confirmed that this vessel can reduce a weak magnetic field to -100 dB or 1/10⁵. The size of this vessel is 32 cm in diameter, 64 cm in depth and 2.5 cm in thickness. The shielding effect of the vessel does not decrease even at a low frequency like 0.2 Hz. The high attenuation ratio in the low frequency range indicates that magnetic shielding using a high-T_c superconductor is promising for neuromagnetic measurements with SQUID.     

Calculation of properties of the ozone molecule by the multiconfigurational self-consistent field method

For the ground state of the ozone molecule, by using the multiconfigurational self-consistent field method, we calculated the electric and magnetic properties — quadrupole moment, polarizability, tensor of magnetic susceptibility, nuclear quadrupole interaction constant, and the rotational g-factor. Qualitative agreement between the calculated parameters and experimental values was obtained. The tensors of chemical shielding in the spectrum of the nuclear magnetic resonance for the ¹⁷O isotopes have also been predicted (without allowance for the contribution made by the spin of the electrons). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 713–716, November–December, 2005.     

Die Reaktion10B(d,α)8Be im Energiebereich von 0,5 bis 2 MeV

The differential magnetic susceptibility X=X′-iX″ of HoCl₃, Ho(Y)Cl₃, and Ho(La)Cl₃ has been measured with a mutual inductance bridge with frequencies from 5.3 c/s to 5.12 kc/s at temperatures between 1.1 and 4.2 °K, and in constant magnetic fields up to 3 kOe. — In monoclinic HoCl₃ a magnetic transition has been observed atT=2.15 °K (maximum of X″). No transition occurs for 0.5 and 5% Ho³⁺ in isomorphic YCl₃. — The results for nominal concentrations of 1, 2, and 5% Ho³⁺ in hexagonal LaCl₃ indicate, that there is a considerable precipitation of monoclinic HoCl₃ during crystal growth. Relaxation measurements on Ho³⁺ in hexagonal sites are interpreted in terms of a phonon-bottleneck in the temperature region 1.1 °K≦T≦2.0⁰K with a hot-phonon equilibration time of about 0.2 μs.     

High-precision evaluation of the magnetic moment of the helion

NMR spectra of samples containing a mixture of hydrogen deuteride HD with pressure of about 80 atm and helium-3 with partial pressure of about 1 atm are analyzed. The ratio of the resonance frequencies of the nuclei, F(³He)/F(H₂), is determined to be 0.761786594(2), which is equal to the magnetic moment of the helion (bound in a helium atom) in the units of the magnetic moment of a proton (bound in molecular hydrogen). The uncertainty of two digits in the last place corresponds to a relative error of ??[F(³He)/F(H₂)] = 2.6 × 10^?9. The use of the known calculated data on the shielding of nuclei in the helium-3 atom (??(³He) = 59924(2) × 10^?9) and on the shielding of protons in hydrogen (??(H₂) = 26288(2) × 10^?9) yields a value of ??(³He)/?? _p = ?0.761812217(3) for the free magnetic moment of the helion in the units of the proton magnetic moment.     

Density-dependent magnetic shielding in gas phase 13C N.M.R.

Density-dependent ¹³C nuclear magnetic shielding has been found for each of the pure gases CH₄, C₂H₆, C₂H₄, CO and CO₂, and for several binary mixtures of gases. For methane gas the density dependence is greater at higher temperatures in contrast to expectation and the observed temperature dependence of the shielding at zero density is attributable to nuclear motion. ¹³C magnetic shielding is considerably higher in the gas phase than in the liquid phase and the difference varies for chemically non-equivalent ¹³C nuclei by amounts which are well above the level of experimental error.     

A Remark on Pople's Induced Current Theory

A very widely known and widely used ^[1] expression to calculate a nuclear magnetic shielding constant by combining the effect of diamagnetic and paramagnetic atomic currents on each atom was given by Pople. ^[2,3] In the present article, we will present a remark on a restriction to the applicablity of Pople's induced current theory. ^[2,3] To simplify the discussion, we will deal with a simple hydride MH, in which paramagnetic circulation can occur only in the atom M. The rectangular coordinates x, y and z are taken as Fig. 1.     

135Ba and137Ba Fourier transform NMR and NQR studies

¹³⁵Ba and¹³⁷Ba Fourier transform nuclear magnetic resonance and nuclear quadrupole resonance investigations are reported in liquids resp. solids. From these measurements ratios of g₁-factors, hyperfine structure anomalies, magnetic moments, atomic shielding constants and the ratio of the quadrupole moments are evaluated using also data from literature.     

Multiple-magnetic field 139La NMR and density functional theory investigation of the solid lanthanum(III) halides

Results from a solid-state ¹³⁹La NMR spectroscopic investigation of the anhydrous lanthanum(III) halides (LaX₃; X=F, Cl, Br, I) at applied magnetic fields of 7.0, 9.4, 11.7, 14.1, and 17.6 T are presented and highlight the advantages of working at high applied magnetic field strengths. The ¹³⁹La quadrupolar coupling constants are found to range from 15.55 to 24.0 MHz for LaCl₃ and LaI₃, respectively. The lanthanum isotropic chemical shifts exhibit an inverse halogen dependence with values ranging from −135 ppm for LaF₃ to 700 ppm for LaI₃, which represents nearly half of the total lanthanum chemical shift range. The spans of the magnetic shielding tensors also vary widely, from 35 to 650 ppm for the solid LaF₃ through LaI₃. DFT calculations of the ¹³⁹La electric field gradient and magnetic shielding tensors have been performed and provide a qualitative interpretation of the trends observed experimentally.     

Rapid,Microwave‐Assisted,and One‐Pot Synthesis of Magnetic Palladium–CoFe2O4–Graphene Composite Nanosheets and Their Applications as Recyclable Catalysts

Here, a microwave‐assisted approach has been demonstrated to rapidly prepare magnetic Pd–CoFe₂O₄–graphene (GE) composite nanosheets in ethylene glycol (EG) solvent. The generation of both Pd and CoFe₂O₄ nanoparticles is accompanied with the reduction process of graphene oxide (GO) by EG. The surface morphologies and chemical composition of the composite nanosheets are characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray spectrometer (EDS), powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) measurements. The as‐prepared Pd–CoFe₂O₄–GE composite nanosheets exhibit a remarkable catalytic activity towards the reduction of 4‐nitrophenol by sodium borohydride (NaBH₄) at room temperature. The apparent kinetic rate constant (K _app) of this catalytic reaction could reach about 11.0 × 10^?3 s^?1. Moreover, the CoFe₂O₄ component exhibits a magnetic property, which could make the Pd–CoFe₂O₄–GE composite nanocatalysts separated from the suspension system. The catalytic conversion of the 4‐nitrophenol to 4‐aminophenol could reach 87.2% after four cycles. This work presents a simple, rapid, and versatile method to fabricate both metal and spinel‐type complex oxides on GE nanosheets, providing a new opportunity for their applications in the recyclable catalytic reaction.     

Proton shielding function for hydrogen chloride

For a diatomic molecule the nuclear shielding constant σ(ξ) of either nucleus can be expanded as a power series in the relative displacement from equilibrium ξ. Thus the nuclear shielding function is

where ξ=(r-r _e)/r _e with r the actual bond length and r _e the equilibrium bond length. The σ_e ⁽ⁱ⁾ are molecular parameters. By experimental observation of the temperature dependence of the proton magnetic shielding of hydrogen chloride gas it is possible, after allowing for intermolecular effects, to obtain the values σ_e ⁽⁰⁾=32·48 (±0·33) p.p.m. and σ_e ⁽¹⁾=-100 (±24) p.p.m. for the coefficients of the proton shielding function. Using this data it is possible to show that the isotope shift between H³⁷Cl and H³⁵Cl is about 0·001 p.p.m. By a comparison with earlier results for molecular hydrogen it would appear that in some instances differences in vibrational and rotational averaging may alter chemical shifts between different compounds by amounts considerably larger than the experimental error in chemical shift measurement.     

High resolution nuclear magnetic resonance spectroscopy in liquids and gases at pressures up to 2500 bar: II. Density dependence of the proton magnetic shielding constants in the nonpolar gases methane and ethylene

The density dependence of the proton magnetic shielding constant σ in methane and ethylene has been investigated experimentally using a high resolution spectrometer which operates with hydrostatic pressures between 0 and 2500 bar. At a constant temperature of 29.2°C a nonlinear dependence of σ on the density ? has been observed for both CH₄ and C₂H₄ in density intervals from 0–575 amagat and 0–475 amagat, respectively. Using the same apparatus the diamagnetic molar susceptibilities of the two gases have also been determined. The experimental results are discussed theoretically by comparing the observed variations of the shielding constants to the values calculated with theoretical models taken from literature.     

The effect of doping three Al and N atoms on the chemical shielding tensor parameters of the boron phosphide nanotubes: A DFT study

In this work, an armchair model of the (4,4) boron phosphide nanotubes (BPNTs) with a 1-nm length and consisting of 32 B and 32 P atoms is considered to study the influence of doping three atoms of aluminum in sites of boron (B_3AlPNTs) and three atoms of nitrogen in sites of phosphors (BP_3NNTs) on the electrostatic structure properties. The mouths of nanotubes are capped by hydrogen atoms in order to saturate the dangling bonds of the boundaries and to decrease the calculation time. The structures of BPNTs, B_3AlPNTs and BP_3NNTs are optimized by performing the level of density functional theory (DFT) using 6-31G^? basis set. The optimized structures are used for calculating the chemical shielding (CS) tensors and nuclear magnetic resonance parameters such as isotropic chemical shielding (CS^I) and anisotropic chemical shielding (CS^A). The results reveal that in both models of B_3AlPNTs and BP_3NNTs by doping N atoms the chemical shielding parameters of P and B atoms, which are directly connected to the Al and N atoms decreased and the other sites significantly changed.     

High-resolution rotational spectrum of methyl cyanide

The ground-state microwave spectrum of methyl cyanide is remeasured between 70 and 240 GHz with a molecular beam spectrometer and by use of the Lamb dip method. It allows us to determine with great accuracy the B rotational constant, the quartic and sextic centrifugal distortion constants, the nuclear quadrupole coupling constant, and the spin-rotation constants of nitrogen. The magnetic shielding constants of nitrogen are also determined.