M. Kiritani et al., INTRAMOLECULAR RADIATIONLESS TRANSITIONS IN SUBSTITUTED BENZALDEHYDES, Journal of physical chemistry, 98(44), 1994, pp. 11265-11268
Phosphorescence excitation spectra of benzaldehyde and its derivatives
have been observed in supersonic jets. We have also observed the disp
ersed phosphorescence spectrum of benzaldehyde and found the intramole
cular vibrational redistribution (IVR) in the triplet manifold. The fa
st radiationless transitions in aromatic carbonyl molecules are induce
d by the interactions among four electronic states, that is, S-1(1)(n
pi), 3(pi pi*), 3(n pi*), and the S-0 ground state. Particularly, the
change in the vibronic coupling between the (3)(pi pi) and (3)(n pi*
) states is important for the substitution effect. In the halogen and
methyl-substituted benzaldehydes, the vibronic bands were found to be
remarkably weakened. It is considered to be due to the dilution of the
(3)(n pi) levels by the nonphosphorescent (3)(n pi pi*) levels and t
he coupling with the ground state. In 4-pyridinecarboxaldehyde, howeve
r, the intersystem crossing (ISC) is relatively slow because the 3(pi
pi) energy is higher and the coupling with the S-1(1)(n pi*) state is
not strong compared with that of benzaldehyde.