Basics of NMR line shape in quasicrystals

The measurement and analysis of broad nuclear magnetic resonance (NMR) spectra of quasicrystals require experimental methods and theoretical interpretations different from NMR investigations of regular periodic crystals. Frequency- and field-sweep methods for recording quasicrystalline NMR spectra are described and compared with the measurement of²⁷Al NMR spectra of icosahedral AlPdMn and decagonal AlNiCo quasicrystals. The nuclear spin interactions that determine the NMR line shape are the same for both types of the above Al-based quasicrystals, where the electric quadrupolar interaction with the broad distribution of its electric field gradient parameters predominantly determines the shape of the broad satellite “background” intensity. The essential observations are an almost isotropic²⁷Al NMR spectrum of the icosahedral quasicrystals and a strong angular dependence of the spectrum of decagonal quasicrystals.     

NMR Studies of Hindered Rotation. The Diels-Alder Adduct of 4-Methyl-1, 2, 4-triazoline-3, 5-dione with Phencyclone: Restricted Motion of Unsubstituted Bridgehead Phenyls.

4-Methyl-1, 2, 4-triazoline-3, 5-dione was produced by lead tetraacetate oxidation of 4-methylurazole and allowed to react with phencyclone, 1-The resulting Diels-Alder adduct, 2, has been characterized by one-and two-dimensional ¹H and ¹³C NMR at 300 and 75 MHz, respectively, at ambient temperatures in different solvents. The NMR data are consistent with hindered rotation of the bridgehead unsubstituted phenyl groups about the C(sp²)-C(sp³) bonds, based on numbers of absorption signals in the ¹H and ¹³C NMR aryl region, together with magnetic anisotropic effects in the ¹H spectrum. The spectral simplicity suggests further that stereochemistry at the ring junction nitrogens involves only a single isomer or very rapidly interconverting “exo”/“endo” isomers (if the ring junction nitrogens are pyramidalized).     

NMR investigation of monodomain formation in a weak ferromagnet FeBO3

Process of monodomain formation in FeBO₃ antiferromagnet in the static magnetic field applied in the magnetically easy plane is studied by NMR technique at the temperatures 4.2 and 77 K. It is found that the⁵⁷Fe NMR signal splits into three absorption lines. Dependence of the intensities and the resonance frequency changes of the “central” and of the “side” signals on the static field amplitude is investigated. It is shown that the observed effects are determined both by layered character of domain structure and weak ferromagnetism of iron borate. Possible utilizations of method (based on the NMR frequency differences of nuclei in different domains in the static magnetic field) for investigation of the domain structure character and the remagnetization dynamics of magnetically ordered materials are discussed.     

Statics and dynamics of the modulation in incommensurate Rb2ZnBr4 as detected by NMR

The dynamics of the incommensurate modulation of Rb₂ZnBr₄ is investigated near the transition to the normal high-temperature phase using first-order quadrupole effects in nuclear magnetic resonance (NMR).⁸⁷Rb NMR spectra and two-dimensional⁸⁷Rb NMR exchange spectra are reported. All results can be described consistently in terms of a static modulation in the incommensurate phase without any indication for “floating” or large-scale fluctuations of the modulation wave. The spectra taken about 135 K below T_i in the lower incommensurate phase well above the soliton regime show no indication for the existence of a higher-order commensurate modulation in Rb₂ZnBr₄.     

Determination of Reorientation Angles from Two-Dimensional Exchange Spectra of Powders in Radiospectroscopy

A method for transforming a 2D exchange spectrum into an orientation representation is proposed which is based on finding the reorientation probability as a function of angles. A procedure of evaluation and analysis of two-dimensional magnetic spectra of powders is described and a method for finding the asymmetry parameter from 2D exchange spectra is proposed. The capabilities of the method are illustrated for a model ³⁵Cl 2D nutation exchange NQR spectrum of chloral hydrate CCl₃CH(OH)₂ and an experimental ¹³C 2D exchange NMR spectrum of dimethylsulphone CH₃–SO₂–CH₃. The asymmetry parameter of the chemical shift tensor for this compound is determined.     

Magnetic “doublets” in Mössbauer spectra of superparamagnetic particles

It is shown that the Mössbauer magnetic hfs spectra of a superparamagnetic particle are cardinally affected by the rotation of its magnetic moment about the magnetic anisotropy field. This rotation renormalizes the nuclear g factors and qualitatively transforms the spectra. In particular, apart from the well-known magnetic sextet, five, four, three, and even two (magnetic “doublet”) lines can arise in the ⁵⁷Fe absorption spectra.     

A New Method of Obtaining Structural Information from 2M Exchange NMR and NQR Spectra of Powders

A method of calculating the singularities of two-dimensional correlation spectra of powders and determining the structural parameters with the help of a computer program is described. The opportunities of the method are illustrated on examples of experimental 2M exchange ¹³ C NMR spectra of dimethylsulfone, 2M exchange ² H NMR spectrum of hexamethylbenzene, and model 2M exchange nutational NQR spectrum for spin I = 3/2. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 72–75, August, 2005.     

A New Insight into Cobalt Metal Powder Internal Field 59Co NMR Spectra

The authors present a new approach of internal field ⁵⁹Co NMR spectra assignment leaving apart from “usual” decomposition on “pure” hcp and fcc stackings, and a set of stacking faults (sfs) sf₁–sf₅ with a certain lines position. The authors propose including into consideration not only cobalt structural features as well as its magnetic nature due to the strong ferromagnetism in Co metal. The last fact supposes an existence of different magnetic species such as magnetic domains, domain walls, and single-domain particles, thereby helping to spectral lines assignment according to both structural and magnetic origin. The examined sample contains fcc and hcp resonance peaks in both domains and domain walls giving the hcp to fcc ratio equal to 1.9, as well a significant amount of Co sfs, or Co in loose coordination, up to 10 %. The research exhibits a good agreement of all implemented techniques.     

Parallelizing acquisitions of solid-state NMR spectra with multi-channel probe and multi-receivers: Applications to nanoporous solids

A five-channel (¹H, ¹⁹F, ³¹P, ²⁷Al, ¹³C) 2.5 mm magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is used in combination with three separate receivers for the parallel acquisitions of one (1D) and two-dimensional (2D) NMR spectra in model fluorinated aluminophosphate and porous Al-based metal-organic framework (MOF). Possible combinations to record simultaneously spectra using this set-up are presented, including (i) parallel acquisitions of quantitative 1D NMR spectra of solids containing nuclei with contrasted T₁ relaxation rates and (ii) parallel acquisitions of 2D heteronuclear NMR spectra. In solids containing numerous different NMR-accessible nuclei, the number of NMR experiments that have to be acquired to get accurate structural information is high. The strategy we present here, i.e. the multiplication of both the number of irradiation channels in the probe and the number of parallel receivers, offers one possibility to optimize this measurement time.     

Mechanism of protonic conductivity in an NH4HSeO4 crystal

The chemical exchange of deuterons in a partly deuterated ammonium hydrogen selenate crystal is investigated by deuteron magnetic resonance (²H NMR) spectroscopy over a wide range of temperatures. The changes observed in the line shape of the NMR spectra at temperatures above 350 K are characteristic of chemical exchange processes. The exchange processes are thoroughly examined by two-dimensional ²H NMR spectroscopy. It is established that, over the entire temperature range, only deuterons of hydrogen bonds are involved in the exchange and the rates of exchange between deuterons of all types are nearly identical. No deuteron exchange between the ND₄ groups and hydrogen bonds is found. A new model of proton transport in ammonium hydrogen selenate is proposed on the basis of the experimental data. This model makes it possible, within a unified context, to explain all the available experimental data, including macroscopic measurements of the electrical conductivity.     

The NMR-WEBLAB: An internet approach to NMR lineshape analysis

The nuclear magnetic resonance (NMR) WEBLAB is described, providing an interactive tool for analyzing NMR spectra of solids and anisotropic liquids to elucidate their molecular dynamics. It is a collection of programs freely available over the Internet at http://www.mpip-mainz.mpg.de/weblab40/that permit the interpretation of one-dimensional NMR spectra in the case of motions occurring on a cone and of two-dimensional exchange NMR data for discrete jumps. The programs are described in detail and analytical formulae for the averaged interaction tensor components that govern the spectra in the fast motional limit are derived in an appendix. To facilitate the validation of the results obtained from the WEBLAB, we present examples for two- and three-site jumps and demonstrate how WEBLAB can be utilized for analyzing more complex motions around more than one axis as met, e.g., in poly(diethysiloxane), where experimental data are available.     

Ensemble of single quadrupolar nuclei in rotating solids: sidebands in NMR spectrum

A novel way is proposed to describe the evolution of nuclear magnetic polarization and the induced NMR spectrum. In this method, the effect of a high-intensity external static magnetic field and the effects of proper Hamiltonian left over interaction components, which commute with the first, are taken into account simultaneously and equivalently. The method suits any concrete NMR problem. This brings forth the really existing details in the registered spectra, evoked by Hamiltonian secular terms, which may be otherwise smoothed due to approximate treatment of the effects of the secular terms. Complete analytical expressions are obtained describing the NMR spectra including the rotational sideband sets of single quadrupolar nuclei in rotating solids.     

Internal magnetic fields in submicron particles of barium hexaferrite detected by 57Fe NMR

⁵⁷Fe nuclear magnetic resonance (NMR) spectra of hexaferrite BaFe₁₂O₁₉ powder samples prepared by glass crystallization method were measured at 4.2 K and analyzed in comparison to spectra of single crystals. Samples with various mean particle dimensions were tested. NMR spectral lines corresponding to individual iron sublattices showed pronounced frequency shifts of their positions and a significant line broadening compared to single crystals. The significant contribution to the line shifts and line shape had a uniform macroscopic origin giving identical absolute value of shifts and the same line shapes for all measured lines of a particular sample. Estimations of demagnetization fields based on mean particle dimensions reasonably corresponded to the observed frequency shifts for particle mean diameter 67 nm, or had a higher value for a sample with mean diameter of 340 nm, for which a presence of domain walls was detected by NMR. In the spectrum of a sample with the smallest particles (～16 nm), an additional contribution having broader lines and faster spin-spin relaxations was found. It could be assigned to weaker exchange interactions or deviations of magnetic moment directions from the hexagonal axis in a surface layer.     

Pure-exchange solid-state NMR

Three exchange nuclear magnetic resonance (NMR) techniques are presented that yield (13)C NMR spectra exclusively of slowly reorienting segments, suppressing the often dominant signals of immobile components. The first technique eliminates the diagonal ridge that usually dominates two-dimensional (2D) exchange NMR spectra and that makes it hard to detect the broad and low off-diagonal exchange patterns. A modulation of the 2D exchange spectrum by the sine-square of a factor which is proportional to the difference between evolution and detection frequencies is generated by fixed additional evolution and detection periods of duration tau, yielding a 2D pure-exchange (PUREX) spectrum. Smooth off-diagonal intensity is obtained by systematically incrementing tau and summing up the resulting spectra. The related second technique yields a static one-dimensional (1D) spectrum selectively of the exchanging site(s), which can thus be identified. Efficient detection of previously almost unobservable slow motions in a semicrystalline polymer is demonstrated. The third approach, a 1D pure-exchange experiment under magic-angle spinning, is an extension of the exchange-induced sideband (EIS) method. A TOSS (total suppression of sidebands) spectrum obtained after the same number of pulses and delays, with a simple swap of z periods, is subtracted from the EIS spectrum, leaving only the exchange-induced sidebands and a strong, easily detected centerband of the mobile site(s).     

<Superscript>1</Superscript>H and<Superscript>13</Superscript>C chemical shift assignments and stereochemistry of matrine and oxymatrine

Matrine and oxymatrine were extracted fromSophora flavescens, and their¹H and¹³C nuclear magnetic resonances (NMR) were unambiguously assigned by a combination of different two-dimensional 2-D¹H-¹³C and¹H-¹H correlation experiments of HMQC, HMQC-TOCSY and MAXY. The technique of using those experiments to make the assignment of the heavily overlapped spectrum is demonstrated. The coupling constants of matrine were measured by 2-DJ-resolved spectrum and 1-D spectra extracted from the slices of 2-D MAXY spectrum. The stereochemistry of the titled compounds was established from the NMR spectroscopy.     

NMR Studies of Hindered Rotation and Magnetic Anisotropy: The Diels–Alder Adducts of Phencyclone with N‐Phenylmaleimide and N‐(2‐Trifluoromethylphenyl)maleimide. Ab Initio Calculations for Optimized Structures

Abstract

N‐Phenylmaleimide, 2, and N‐(2‐trifluoromethylphenyl)maleimide, 3, were separately added to phencyclone, 1, to yield the corresponding phencyclone Diels–Alder adducts, 4 and 5. The resulting adducts (and some precursors) have been characterized by one‐ and two‐dimensional ¹H and ¹³C NMR at 300 and 75 MHz, and by ¹⁹F NMR at 282 MHz, at ambient temperatures. The NMR data are consistent, for both adducts, with: (a) hindered rotation of the bridgehead unsubstituted phenyl groups about the C(sp²)–C(sp³) bonds, based on slow exchange limit (SEL) spectra and (b) endo adduct configuration based on magnetic anisotropic effects in the ¹H NMR. The NMR spectra of the phencyclone adduct, 4, of N‐phenylmaleimide, indicate free rotation on the NMR timescales (fast exchange limit, FEL spectra) about the N‐phenyl bond. The spectra for the adduct, 5, of N‐(2‐trifluoromethylphenyl)maleimide are interpreted as consistent with SEL regimes, for the N‐aryl rotations, with a single rotamer present in which the trifluoromethyl group is directed “out of” the adduct cavity, and away from the phenanthrenoid moiety. This conclusion is based, in part, on NMR data suggesting the apparent slow N‐aryl bond rotation in a pair of atropisomers corresponding to the acetic acid addition products from the N‐(2‐trifluoromethylphenyl)maleimide. Evidence of magnetic anisotropic effects due to the phenanthrenoid moiety and proximal carbonyls is discussed. ¹H, ¹³C, and ¹⁹F assignments are presented and interpreted. Molecular modeling calculations at the Hartree–Fock level, 6‐31G* basis set, were performed to provide geometry optimizations for energy‐minimized structures of selected compounds.     

Macroscopic quantum effects observed in Mössbauer spectra of antiferromagnetic nanoparticles

The ⁵⁷Fe Mössbauer spectra of antiferromagnetic nanoparticles have been measured for almost half a century and often displayed a specific (non-superparamagnetic) temperature evolution of the spectral shape which looks like a quantum superposition of well-resolved magnetic hyperfine structure and single line or quadrupolar doublet of lines with the temperature-dependent partial spectral areas. We have developed a quantum-mechanical model for describing thermodynamic characteristics of an ensemble of ideal and “uncompensated” antiferromagnetic nanoparticles with uniaxial magnetic anisotropy in the first approximation of slowly relaxing macrospins of magnetic sublattices. This model allows one to qualitatively describe the macroscopic quantum effects observed in the Mössbauer spectra and to clarify principally the difference in thermodynamic properties of ferromagnetic and antiferromagnetic particles revealed in spectroscopic measurements.     

Automatic computer simulations of ESR spectra

A versatility of automatic ESR simulation procedures has been developed to obtain high quality of fitting and produce additional information. The following examples are treated: derivation of long-range proton hyperfine coupling constants from unresolved lines; determination of¹³C hf couplings from the naturally abundant isotope satellites; analyzing chemical exchange phenomena with two-sites model; decomposition of superimposed spectra consisting of poorly resolved components. In order to achieve best agreement between calculated and experimental spectra within a reasonable number of iteration cycles, we combined various approaches, like consecutive independent parameter optimization, least-square approach, optimization on “serpentines” and optimization of compound parameters. The spectra can be computed both for liquid and solid state samples, for non-oriented, partially oriented and single crystal samples. Second order perturbation formulas are used for the spin Hamiltonian includingg- and hyperfine tensors that have isotropic, axial and rhombic symmetry. For chemical exchange the modified Bloch equation for two-site model is used. Various lineshapes, including Lorentzian, Gaussian, mixed, modulation and dispersion distorted forms are applied. Third order parabolic interpolations are used for building up spectra from individual lines. In order to correct sweep non-linearity a third order interpolation converts the spectrum to become equidistant. This procedure can occasionally improve square deviation by an order of magnitudes for well resolved spectra. In the analysis of strongly overlapping superimposed spectra, simultaneous adjustment of two independent experimental spectra can give an exact decomposition. The inclusion of long-range couplings offers highly perfect fitting and allows one to resolve contributions of naturally abundant¹³C isotopes.     

Two-dimensional electron-hole liquid in the strong magnetic field

The Matsubara diagram technique is used to study the formation and thermodynamic properties of an electron-hole liquid (EHL) in the two-dimensional system in the transverse strong magnetic field. The system has discrete energy spectra, i.e. a motion of particles becomes “zero-dimensional”. Therefore, the exchange interaction alone is sufficient to form EHL, the correlation correction being negligible.