Optische Kern-Spin-Polarisation in Molekül-Kristallen

This paper deals with the polarisation of nuclei in molecular crystals due to their hyperfine interaction with optically excited triplet states and excitons, a phenomenon which is termed optical nuclear polarisation (ONP). A theory is presented which extends the mechanisms of dynamic nuclear polarisation (Overhauser effect) to the case of spin systems containing triplet states with S = 1 and nuclei with I = 1/2. In this mechanisms the optical electron polarisation (OEP) caused by symmetry selection rules for intersystem crossing to and from the magnetic triplet sublevels is assumed to be transferred to the nuclear magnetic substates by efficient hyperfine relaxation transitions. The adiabatic fast passage is used to detect the nuclear polarisation. The advantages and conditions of this technique as compared to other nmr techniques are discussed. ONP results at room temperature are given as a function of the external field H0, its orientation with respect to the crystalline axes, the intensity and frequency of the exciting light and the concentration and types of guest molecules. In phenazine crystals relative polarisation factors up to 50 are found with marked orientation dependencies even in fields as high as 11 kG. These results can be interpreted in principle in terms of the presented theory. However, in low fields (0 - 200 G) where ONP caused by hyperfine relaxation vanishes, large polarisations are found in doped crystals of fluorene and anthracene. The maximum absolute polarisation in fluorene doped with acridine is 3.6 · 10-4 at H0 = 80 G corresponding to a relative polarisation factor of ~ 104. The effect of doping is discussed.. Reference is made to a possible ONP mechanism 3 which is able to produce large nuclear polarisations at low field