On the Origin of the Shift Between Vertical Excitation and Band Maximum in Molecular Photoabsorption - Aix-Marseille Université Access content directly
Journal Articles Journal of Molecular Modeling Year : 2020

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

Abstract

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.
Fichier principal
Vignette du fichier
p145_bai_shift_jmm_2020.pdf (745.48 Ko) Télécharger le fichier
Origin : Publication funded by an institution
Loading...

Dates and versions

hal-02612358 , version 1 (19-05-2020)

Licence

Attribution

Identifiers

Cite

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⟩
75 View
54 Download

Altmetric

Share

Gmail Facebook X LinkedIn More