Relative magnitudes of singlet and triplet state dipole moments: the lowest nπ* excited states of p-methylbenzaldehyde and p-chlorobenzaldehyde

Abstract

The molecular dipole moment changes upon 1nπ* and 3nπ* excitation of p-methylbenzaldehyde and p-chlorobenzaldehyde isolated in p-dimethoxybenzene host crystals have been determined from measurements of the Stark splittings in phosphorescence excitation and phosphorescence spectra. Within the experimental uncertainty, the changes are identical for the corresponding triplet and singlet states. This result contrasts with similar determinations for formaldehyde, benzophenone, and 4,4′-dichlorobenzophenone and with predictions based on simple molecular orbital and electron correlation arguments. The result is considered to be a consequence of a relatively large mixing of 3nμ* and 3μμ* states.