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

ABSTRACT: For benzene, toluene, aniline, fluorobenzene, and phenol, even sophisticated treatments of electron correlation, such as MRCI and XMS-CASPT2 calculations, show oscillator strengths typically lower than experiment. Inclusion of a simple pseudo-diabatization approach to perturb the S₁ state with approximate vibronic coupling to the S₂ 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 S₁ and S₂ states is strong at the S₀ 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

SUBMITTER: Robinson D 

PROVIDER: S-EPMC8279645 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature