Tailored anharmonic–harmonic vibrational profiles for fluorescent biomarkers

We propose a hybrid anharmonic–harmonic scheme for vibrational broadenings, which embeds a reduced-space vibrational configuration interaction (VCI) anharmonic wave function treatment in the independent-mode displaced harmonic oscillator (IMDHO) model. The resulting systematically-improvable VCI-in-IMDHO model allows including the vibronic effects of all vibrational degrees of freedom, while focusing the effort on the important degrees of freedom with minimal extra computational effort compared to a reduced-space VCI treatment. We show for oligothiophene examples that the VCI-in-IMDHO approach can yield accurate vibrational profiles employing smaller vibrational spaces in the VCI part than the reduced-space VCI approach. By this, the VCI-in-IMDHO model enables accurate calculation of vibrational profiles of common fluorescent dyes with more than 100 vibrational degrees of freedom. We illustrate this for three examples of fluorescent biomarkers of current interest. These are the oligothiophene-based fluorescent dye called HS84, 1,4-diphenylbutadiene, and an anthracene diimide. For all examples, we assess the impact of the anharmonic treatment on the vibrational broadening, which we find to be more pronounced for the intensities than for the peak positions.