Substituent effects in the absorption spectra of phenol radical species: origin of the redshift caused by 3,5-dimethoxyl substitution

Abstract

The ground-state equilibrium geometries, electronic structures and vertical excitation energies of methyl- and methoxyl-substituted phenol radical cations and phenoxyl radicals have been investigated using time-dependent density-functional theory (namely TD-B3LYP) and complete-active-space second-order perturbation theory (CASPT2). The "anomalous" large redshifts of the absorption maxima of the phenol radical species observed in the ultraviolet-visible spectral region upon di-meta-methoxyl substitution are reproduced by the calculations. Furthermore, these "anomalous" shifts which were unexplained to date can be rationalized on the basis of a qualitative molecular orbital perturbation analysis.