On the Origin of the Shift Between Vertical Excitation and Band Maximum in Molecular Photoabsorption

Shuming Bai (1) , Ritam Mansour (1) , Ljiljana Stojanović (1) , Josene Toldo (1) , Mario Barbatti (1)

1 ICR - Institut de Chimie Radicalaire

The analysis of the photoabsorption spectra of molecules shows that the band maximum is usually redshifted in comparison to the vertical excitation. We conducted a throughout analysis of this shift based on low-dimensional analytical and numerical model systems, showing that its origin is rooted in the frequency changing between the ground and the excited states in multidimensional systems. Moreover, we deliver a benchmark of ab initio results for the shift based on a comparison of vertical excitations and band maxima calculated with the nuclear ensemble approach for the 28 organic molecules in the Mülheim molecular dataset. The mean value of the shift calculated over 60 transitions is 0.11 ± 0.08 eV. The mean value of the band width is 0.32 ± 0.14 eV.

Keywords: Spectrum simulation; Vertical excitations; Excited states; Absorption cross-section 2

Domains: Theoretical and/or physical chemistry

Shuming Bai, Ritam Mansour, Ljiljana Stojanović, Josene Toldo, Mario Barbatti. On the Origin of the Shift Between Vertical Excitation and Band Maximum in Molecular Photoabsorption. Journal of Molecular Modeling, 2020, 26 (5), ⟨10.1007/s00894-020-04355-y⟩. ⟨hal-02612358⟩