CH3 spin probe in solid Kr: Matrix structure and guest-host interaction

Experimental EPR data obtained for the methyl, CH3, radical trapped in quench condensed solid Kr are analyzed rendering the radical a probe for determination of regional disorder in Kr and similar solid matrices. Formation of regions of a highly disordered local matrix structure is proved. An attempt is presented of assessing a disorder parameter, based on the line broadening. The new structure is shown to be very effective in accumulating the radicals which are transiently mobile at the Kr 4.2 K surface. We discuss a model of the trapped radical rotation, which includes somewhat different mechanism than the hindrance of the rotation about the C3 axis and the rotation about the in-plane C2 axes. The level of the thermal contact of the radical spin-rotation motion with the lattice degrees of freedom in regions of varying order in the Kr solid matrix was assessed by progressive saturation curve-fitting parameters related to the spin-lattice relaxation time T1 of the radical.