Benzene, Toluene, and Monosubstituted Derivatives: Diabatic Nature of the Oscillator Strengths of S1 → S0 Transitions

For benzene, toluene, aniline, fluorobenzene, and phenol, even sophisticated treatments of electron con-elation, such as MRCI and XMS-CASPT2 calculations, show oscillator strengths typically lower than experiment. Inclusion of a simple pseudo-diabatization approach to perturb the S-1 state with approximate vibronic coupling to the S-2 state for each molecule results in more accurate oscillator strengths. Their absolute values agree better with experiment for all molecules except aniline. When the coupling between the S-1 and S-2 states is strong at the So geometry, the simple diabatization scheme performs less well with respect to the oscillator strengths relative to the adiabatic values. However, we expect the scheme to be useful in many cases where the coupling is weak to moderate (where the maximum component of the coupling has a magnitude less than 1.5 au). Such calculations give an insight into the effects of vibronic coupling of excited states on UV/vis spectra.

Automated summary

This study investigates the oscillator strengths of benzene, toluene, aniline, fluorobenzene, and phenol, finding that a simple pseudo-diabatization approach can improve accuracy, especially in cases of weak to moderate coupling.