ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Solid-state NMR signal enhancements of about two orders of magnitude (100–400) have been observed in dynamic nuclear polarization (DNP) experiments performed at high magnetic field (5 T) and low temperature (10 K) using the nitroxide radical 4-amino TEMPO as the source of electron polarization. Since the breadth of the 4-amino TEMPO EPR spectrum is large compared to the nuclear Larmor frequency, it has been assumed that thermal mixing (TM) is the dominate mechanism by which polarization is transferred from electron to nuclear spins. However, theoretical explanations of TM generally assume a homogeneously broadened EPR line and, since the 4-amino TEMPO line at 5 T is inhomogeneously broadened, they do not explain the observed DNP enhancements. Accordingly, we have developed a treatment of DNP that explicitly uses electron–electron cross-relaxation to mediate electron–nuclear polarization transfer. The process proceeds via spin flip–flops between pairs of electronic spin packets whose Zeeman temperatures differ from one another. To confirm the essential features of the model we have studied the field dependence of electron–electron double resonance (ELDOR) data and DNP enhancement data. Both are well simulated using a simple model of electron cross-relaxation in the inhomogeneously broadened 4-amino TEMPO EPR line. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1346640
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