Relaxation mechanisms of the Zeeman sublevels of the phosphorescent triplet state of pyrazine at 1·6K

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Abstract
The observed change in the phosphorescence decay of the spin-aligned triplet state of pyrazine at 1·6K upon application of a magnetic field is examined both experimentally and theoretically. Experimentally, the decay curve is resolved into the three decay components of the three triplet sublevels in the field range of 0–6000 G. Both the decay constants and the fraction of total initial intensity of each decay component are determined for each field strength. Theoretically, the observed change in the decay characteristics is assumed to be solely due to the Zeeman mixing of the zero-field levels in the absence of spin-lattice relaxation processes. This has the effect of distributing the radiative strength of the strongly radiative zero-field level among the other two weakly radiative zero field levels. A simple approximate calculation gives excellent and encouraging agreement with experimental quantities in the range of validity of the approximations made (below 1000 G). A rigorous calculation was then performed using the exact solution of the secular equation resulting from the Hamiltonian including the spin-spin and Zeeman interactions. Due to the difficulty in finding a host of known crystal structure in which pyrazine can dissolve substitutionally and uniquely, the comparison between theory and experiment is made using a polycrystalline sample. A special averaging procedure is used in calculating a theoretical decay curve for each magnetic field strength used. The theoretical decay curve is then decomposed into three components employing the same computer programme used for decomposing the experimental decay curve. The agreement between the observed and the more rigorous calculated decay quantities is excellent up to 2000 G, but observed disagreement appears above 3000 G and increases with field strength. The calculated lifetimes above 3000 G are found to be longer than the observed ones. The difference is due to other relaxation mechanisms at these high fields, for example, in spin-lattice relaxation processes between the Zeeman sublevels of the lowest triplet state.