Magnetic field dependence of the deactivation rates of triplet azocumene in solution

The triplet sensitized photo-decomposition of azocumene into nitrogen and cumyl radicals is investigated by time resolved EPR and optical absorption spectroscopy. It is found that the cumyl radicals carry an initial spin polarization and are formed with a yield that depends on both the solution viscosity and the strength of an external magnetic field. The phenomenon is interpreted in terms of a depopulation-type triplet mechanism, i.e. a competition between decay into radicals and fast, triplet sublevel selective intersystem crossing (ISC) back to the azocumene ground state. Analysis of the data yields relative rate constants for the ISC processes and the cleavage reaction of triplet azocumene. The energetically lower zero field triplet substate is depopulated by ISC about seven times faster than the upper one and about two orders of magnitude faster than depopulation by cleavage occurs. Cleavage probably takes place on the nanosecond time scale, while the ISC must proceed on the picosecond scale, as at elevated viscosity it becomes faster than the rotational Brownian motion of the molecule.     

Thermal conductivity of nonlinear waves in disordered chains

We present computational data on the thermal conductivity of nonlinear waves in disordered chains. Disorder induces Anderson localization for linear waves and results in a vanishing conductivity. Cubic nonlinearity restores normal conductivity, but with a strongly temperature-dependent conductivity κ(T). We find indications for an asymptotic low-temperature κ ∼ T ⁴ and intermediate temperature κ ∼ T ² laws. These findings are in accord with theoretical studies of wave packet spreading, where a regime of strong chaos is found to be intermediate, followed by an asymptotic regime of weak chaos (Laptyeva et al, Europhys. Lett. 91, 30001 (2010)).