ISOTOPE EFFECTS AND PROTON HYPERFINE INTERACTIONS IN THE LOWEST (3)N-PI(ASTERISK) STATE OF SUBSTITUTED BENZALDEHYDES

摘要

The zero-field splittings, principal spin axes, kinetic parameters, and nuclear hyperfine interactions of the (3)n pi* state of p-chloro- and p-methylbenzaldehyde and several of their deuterated derivatives are investigated by zero- and low-field optically detected magnetic resonance (ODMR) at 1.4 K in a p-dimethoxybenzene host. The zero-field splittings show large isotope effects. These are interpreted in terms of spin-orbit interaction with the nearby but higher lying (3) pi pi* state, yielding the energy gap between the two states in both benzaldehyde derivatives. The locations of the spin axes are approximately along the local symmetry axes of the carbonyl group and are insensitive to isotope. But, the spin axis most nearly normal to the plane of a host molecule deviates from the normal by an angle of 7 degrees-13 degrees. The kinetic parameters of the (3)n pi* state also are relatively insensitive to isotope. The dominant hyperfine interactions are associated with the aldehyde hydrogen and indicate that the (3)n pi* state is largely localized on the aldehyde moiety. Various properties of the (3)n pi* and (3) pi pi* states are compared. (C) 1995 American Institute of Physics. [References: 41]