A high precision magnetometer based on pulsed NMR Prigl, R; Haeberlen, U; Jungmann, K ...
Nuclear instruments & methods in physics research. Section A, Accelerators, spectrometers, detectors and associated equipment,
05/1996, Letnik:
374, Številka:
1
Journal Article
Recenzirano
A magnetometer based on pulsed proton magnetic resonance has been developed and constructed. The system will be employed for an accurate measurement of the absolute magnetic field in the region of ...1.45 T in a precision experiment on the muon's anomalous magnetic moment at the Brookhaven National Laboratory (BNL, USA), where a knowledge of the magnetic field is required with 1 × 10
−7 relative accuracy. The performance of the magnetometer has been tested in a large bore superconducting magnet and a precision of one part in 10
8 was achieved.
We demonstrate by selective saturation deuteron NMR experiments on a crystal of selectively deuterated o-terphenyl (OTP) that both end rings I and II attached to the central ring undergo thermally ...activated flip motions. In crystals of OTP, the end rings I and II are not symmetry related, their dynamics can be different and, in fact, is different, although mutual steric hindrance of the rings suggests a strong correlation. We measured the rates k
I
and k
II
of the flips of both end rings I and II as a function of temperature. We find that, independent of the temperature, k
I
exceeds k
II
by roughly a factor of 100. This result excludes correlated flips of rings I and II in the sense that a flip of one ring necessarily entails a flip of the other. The activation energies E
aI
and E
aII
of the two flip processes turn out to be equal (80.5 kJ mol
−1
) within experimental errors. This is taken as a hint that the flips are, after all, related to each other. A mechanism is proposed of how this is possible under the constraint k
I
» k
II
.
Using calcium formate, α-Ca(DCOO)2, as a test sample, we explore how precisely deuteron quadrupole coupling (QC) and chemical shift (CS) tensors Q and σ can currently be measured. The error limits, ...±0.09 kHz for the components of Q and ±0.06 ppm for those of σ, are at least three times lower than in any comparable previous experiment. The concept of a new receiver is described. A signal/noise ratio of 100 is realized in single-shot FT spectra. The measurement strategies and a detailed error analysis are presented. The precision of the measurement of Q is limited by the uncertainty of the rotation angles of the sample and that of σ by the uncertainty of the phase correction parameters needed in FT spectroscopy. With a 4-sigma confidence, it is demonstrated for the first time that the unique QC tensor direction of a deuteron attached to a carbon deviates from the bond direction; the deviation found is (1.2±0.3°). Evidence is provided for intermolecular QC contributions. In terms of Q, their size is roughly 4 kHz. The deuteron QC tensors in α-Ca(DCOO)2 (two independent deuteron sites) are remarkable in three respects. For deuterons attached to sp2 carbons, first, the asymmetry factors η and, second, the quadrupole coupling constants CQ, are unusually small, η1=0.018, η2=0.011, and CQ1=(151.27±0.06) kHz, CQ2=(154.09±0.06) kHz. Third, the principal direction associated with the largest negative QC tensor component lies in and not, as usual, perpendicular to the molecular plane. A rationalization is provided for these observations. The CS tensors obtained are in quantitative agreement with the results of an earlier, less precise, line-narrowing multiple-pulse study of α-Ca(HCOO)2. The assignment proposed in that work is confirmed. Finally we argue that a further 10-fold increase of the measurement precision of deuteron QC tensors, and a 2-fold increase of that of CS tensors, should be possible. We indicate the measures that need to be taken.
The polarization transfer from the para to the ortho/meta deuterons was investigated in a single crystal of perdeuterated biphenyl, C
12D
10. It is demonstrated that this process is due to spin ...diffusion via dipolar coupling. We found that in the range from 290 to 315 K it is strongly dependent on the temperature. The apparent activation energy of about 75 kJ/mol is the same as that of the known 180° flips of phenyl rings about the long molecular axis. As an explanation of the observed temperature dependence of the spin diffusion we discuss an exchange broadening of the relevant zero-quantum line caused by the 180° flips.
The synthesis of a specific isotopomer, C6D4H(ortho)-H(ortho)D4C6 of biphenyl is reported. The intramolecular dipolar coupling of the protons leads to a well-resolved single-crystal proton nuclear ...magnetic resonance (NMR) spectrum and allows one to study the dynamics of the phenyl rings in a unique way. At room temperature and above, the most conspicuous dynamical mode consists of 180° ring flips. The present data together with previous measurements of the total flip rate allow us to conclude that the rings flip almost exclusively independently of each other. Between the incommensurate (IC) phase transition of biphenyl at 38 K andT=250 K, the prominent namical mode consists of oscillatory twists ϕ(t) of the two rings. The data allow us to infer the mean square, (φ2), of these twists. (φ2) is found to grow linearly withT for 50<T<200 K. From the slope of (φ2) vs.T the frequency (the wave number) is derived. The result is cm−1. ForT<38 K, the spectra give direct evidence of the IC phase transition and its nature (stripelike rather than quiltlike). The temperature dependence of the magnitude of the order parameter of the IC phase is obtained.
Solid-state NMR spectroscopy is well established as a method for describing molecular structure with resolution on the atomic scale. Many of the NMR observables result from anisotropic interactions ...between the nuclear spin and its environment. These observables can be described by second-rank tensors. For example, the eigenvalues of the traceless symmetric part of the hydrogen chemical shift (CS) tensor provide information about the strength of inter- or intramolecular hydrogen bonding. On the other hand, the eigenvectors of the deuterium electric field gradient (EFG) tensor give deuteron/proton bond directions with an accuracy rivalled only by neutron diffraction. In this paper the authors report structural information of this type for the amide and carboxyl hydrogen sites in a single crystal of the model peptide N-acetyl-D,L-valine (NAV). They use deuterium NMR to infer both the EFG and CS tensors at the amide and carboxyl hydrogen sites in NAV. Advantages of this technique over multiple-pulse proton NMR are that it works in the presence of {sup 14}N spins which are very hard to decouple from protons and that additional information in form of the EFG tensors can be derived. The change in the CS and EFG tensors upon exchange of a deuteron for a proton (the isotope effect) is anticipated to be very small; the effect on the CS tensors is certainly smaller than the experimental errors. NAV has served as a model peptide before in a variety of NMR studies, including those concerned with developing solid-state NMR spectroscopy as a method for determining the structure of proteins. NMR experiments on peptide or protein samples which are oriented in at least one dimension can provide important information about the three-dimensional structure of the peptide or the protein. In order to interpret the NMR data in terms of the structure of the polypeptide, the relationship of the CS and EFG tensors to the local symmetry elements of an amino acide, e.g., the peptide plane, is essential. The main purpose of this work is to investigate this relationship for the amide hydrogen CS tensor. The amide hydrogen CS tensor will also provide orientational information for peptide bonds in proteins complementary to that from the nitrogen CS and EFG tensors and the nitrogen-hydrogen heteronuclear dipole-dipole coupling which have been used previously to determine protein structures by solid-state NMR spectroscopy. This information will be particularly valuable because the amide hydrogen CS tensor is not axially symmetric. In addition, the use of the amide hydrogen CS interaction in high-field solid-state NMR experiments will increase the available resolution among peptide sites.
Theoretical models for motionally driven spin diffusion are compared and applied to spinsS= 12 andS= 1. Their predictions are quantitatively corroborated by experiments on a single crystal of ...deuterated biphenyl. In this system, a molecular flip process drives spin diffusion and makes it strongly temperature dependent. In the second part, it is shown how spin diffusion of quadrupolar order degenerates into cross relaxation. A single crystal of partially deuterated durene provides a clear-cut example of cross relaxation in a dipolar coupled pair of spinsS= 1. This observation explains why, in solids, the relaxation time of quadrupolar order,T1Q, is often much shorter thanT1.
A detailed description of the diverse mobility of the ND4+ ions in the low-temperature ordered phase of (ND4)2PtCl4 is developed on the basis of single-crystal deuteron NMR spectra and site-selective ...T1 measurements. The ordered phase of (ND4)2PtCl4 consists of two kinds of domains in which the orientation of the ND4+ tetrahedra differs by a 90 degrees rotation about an axis which otherwise is a two-fold symmetry axis of the tetrahedra. Inside the domains, the ND4+ ions do not reorient at low temperatures. The domains are separated by domain walls which contain, according to the deuteron NMR spectra, about 10% of all ND4+ ions. These ions are highly mobile even at 10 K. On rising the temperature, the thickness of the domain walls increases, that is, the ions in more and more layers become mobile. Moreover, we provide evidence for fluctuations of the locations of the domain walls. The central resonance of the domain-wall ions shows a complicated structure below 36 K. On the basis of a tunnelling hypothesis we make an attempt to account for this structure. There are indications that the tunnelling process is incoherent.
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