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 change 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.

Experiments and theory have revealed that hydrogen bonds modify the excited-state lifetimes of nucleosides compared to nucleobases. Nevertheless, how these bonds impact the internal conversion is still unsettled. This work simulates the non-adiabatic dynamics of adenosine conformers in the gas phase with and without hydrogen bonds between the sugar and adenine moieties. The isomer containing the hydrogen bond (syn) exhibits a significantly shorter excited-state lifetime than the isomer without it (anti). However, internal conversion through electron-driven proton transfer between sugar and adenine plays only a minor (although non-negligible) role in the photophysics of adenosine. Either with or without hydrogen bonds, photodeactivation preferentially occurs following the ring-puckering pathways. The role of the hydrogen bond is to avoid the sugar rotation relative to adenine, shortening the distance to the ring-puckering internal conversion.

Recent experimental work revealed that the lifetime of the S3 state of protonated 7-azaindole is about ten times slower than that of protonated 6-azaindole. We simulated the nonradiative decay pathways...

Recent experimental work revealed that the lifetime of the S3 state of protonated 7-azaindole is about ten times slower than that of protonated 6-azaindole. We simulated the nonradiative decay pathways of these molecules using trajectory surface hopping dynamics after photoexcitation into S3 to elucidate the reason for this difference. Both isomers mainly follow a common pp* relaxation pathway involving multiple state crossings while coming down from S3 to S1 in the subpicosecond time scale. However, the simulations reveal that the excited-state topographies are such that while the 6-isomer can easily access the region of nonadiabatic transitions, the internal conversion of the 7-isomer is delayed by a pre-Dewar bond formation with a boat conformation.