Insights for vibronic effects on spectral shapes of electronic circular dichroism and circularly polarized luminescence of aza[7]helicene.

Abstract

We present a systematic study of vibrationally resolved absorption (ABS), electronic circular dichroism (ECD), emission (EMI), and circularly polarized luminescence (CPL) of aza[7]helicene. Because of the rare experience of theoretical CPL calculation, a variety of harmonic models have been employed to compute the vibronic structures. To fully understand the vibronic effects on the spectral shapes, Franck-Condon (FC) and Herzberg-Teller (HT) contributions, Duschinsky mixings and temperature effect have all been taken into consideration. The performance of different alternative approximate methods has been carefully compared and discussed in detail. The results show that Vertical Hessian (VH) model has a slight better performance on the spectral shapes than Adiabatic Hessian (AH), especially for CPL spectrum. The thermal excitation effect has led to a reduced resolution and a broader spectral width. The moderate HT effects on the different spectral shapes have been addressed. The dissymmetry factors have been correctly reproduced and the main vibronic features of the four different spectral shapes have been successfully captured. A good estimation of the overall spectral width, relative position and relative height of different spectral bands has been presented. The nice agreement with the experiment allows us to present a detailed interpretation of the spectral shapes.