A DNP investigation of pi and final sigma transitions for nitroxide spin probes at 1.53 mT

A weak field DNP study of 4-hydroxy-2,2,6, 6-tetramethyl-1-piperidinyloxy (4-hydroxy-TEMPO), 4-amino-2,2,6, 6-tetramethyl-1-piperidinyloxy (4-amino-TEMPO), and 2, 2-Di(4-tert-octylphenyl)-1-picrylhydrazyl (DPPH) free radicals invarious solvents was performed at 1.53 mT using a doubleresonance spectrometer. pi transitions, in which the RF fieldhas a component perpendicular to the static magnetic fieldB0, and final sigma transitions, in which the RF field has a component parallel to B0, were recorded. In order to observe thefinal sigma transitions a new probe head was designed. The final sigma transitions were obtained at the frequencies expected from theoretical calculations. However, the results obtained for the observed enhancements deviated from the values expectedtheoretically.