COOPERATIVE EFFECTS ON THE HS -] LS RELAXATION IN THE [FE(PTZ)6](BF4)2 SPIN-CROSSOVER SYSTEM

The high-spin to low-spin (HS --> LS) relaxation in the [Fe(ptz)6](BF4)2 spin-crossover system deviates strongly from first-order kinetics because of cooperative effects of elastic origin. The shift in horizontal and vertical displacement of the potential wells of the initial and final state relative to each other due to the build-up of an "internal" pressure is estimated from spectroscopic measurements. The HS --> LS relaxation as such is described by the theory of nonadiabatic multiphonon relaxation in the strong-coupling limit, with a Huang-Rhys factor S almost-equal-to 45 which is much larger than the reduced energy gap p. The sigmoidal relaxation curves in [Fe(ptz)6](BF4)2 result when a change in S of almost-equal-to -1 and in p of 1 during the relaxation is taken into account.