Radiofrequency quadrupolar NMR stark spectroscopy: steady state response calibration and tensorial mapping.
Radiofrequency electric (E) fields oscillating at twice the usual NMR frequency (2ω(0)) can induce double-quantum transitions in quadrupolar nuclei, an NMR Stark effect. Characterization of such is of interest to aid understanding of electrostatic effects in NMR spectra. Calibration of Stark responses to an applied electric field may also be used to assess native fields within molecules and materials. We present high-field (14.1 T), room-temperature NMR experiments to calibrate the 2ω(0) Stark response in crystalline GaAs. This system presents an important test of current techniques and conditions, as historical studies at low field (500-900 mT) and low temperature (77 K) provide a basis for comparison. Our measurements of steady state response reveal the quadrupolar Stark tuning rate for (69)Ga in this material. The value, β(Q) = (11.5 ± 0.1) × 10(12) m(-1), is 3.6 times larger than the most-reliable prior result. In the process, we also uncovered a previously unobserved double-quantum steady state coherence. It appears as a completely separable dispersive signal component in quadrature-detected presaturation spectra versus offset from 2ω(0). The new component may eventually afford an independent route to calibrating β(Q). Finally, we demonstrated exceptional agreement with theory of the orientation-dependent Stark response for rotation of the sample relative to B(0) over a range of 90° and for E-field amplitudes from 30-180 V/cm.
Tarasek
Matthew R
MR
Department of Chemistry and Chemical Biology and Center for Biotechnology and Interdisciplinary Studies, Rensselaer Polytechnic Institute, Troy, New York 12180, USA.
Kempf
James G
JG
D001151:Arsenic / Q000737:chemistry*; D005708:Gallium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013696:Temperature
D005708:Gallium; D001151:Arsenic