Vibronic Coupling and Multiple Electronic States Effect in ABS and ECD Spectra: Three [7]Helicene Derivatives.

Vibronic coupling and multiple electronic states effect play a pivotal role in the molecular spectroscopy of large systems. Herein, we present a detailed theoretical study on the absorption (ABS) and electronic circular dichroism (ECD) spectra of three [7]helicene derivatives in chloroform, with a particular emphasis on the significance of vibronic coupling and the multiple electronic states effect in spectral simulations. The vertical gradient (VG) and vertical Hessian (VH) models, incorporating the Franck-Condon (FC) effect and Herzberg-Teller (HT) contribution, are considered in the vibronic calculations. The results indicate that the simulated vibrationally resolved spectra obtained by the VG model combined with the FC effect are more reliable, showing advantages in the rationality of spectral shapes, the accuracy of the relative heights of absorption peaks, and the correctness of positive and negative signals. Reliable predictions of the three [7]helicene derivatives allowed us to further explore the importance of the multiple electronic states effect in the vibrationally resolved spectra, demonstrating that the high-energy electronic excited states, particularly the fifth (S5) and sixth (S6) excited states, are essential for accurately capturing the fine structures observed in the experimental spectra. Our study predicts reliable theoretical reference spectra for the family of [7]helicene derivatives and provides a fundamental understanding of the vibronic coupling of chiral organic molecules with multiple electronic states.