@article{RietzeTitovGranuccietal.2020,
  author    = {Rietze, Clemens and Titov, Evgenii and Granucci, Giovanni and Saalfrank, Peter},
  title     = {Surface hopping dynamics for azobenzene photoisomerization},
  series = {The journal of physical chemistry : C, Nanomaterials and interfaces},
  volume    = {124},
  journal   = {The journal of physical chemistry : C, Nanomaterials and interfaces},
  number    = {48},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1932-7447},
  doi       = {10.1021/acs.jpcc.0c08052},
  pages     = {26287 -- 26295},
  year      = {2020},
  abstract  = {Azobenzenes easily photoswitch in solution, while their photoisomerization at surfaces is often hindered. In recent work, it was demonstrated by nonadiabatic molecular dynamics with trajectory surface hopping [Titov et al., J. Phys. Chem. Lett. 2016, 7, 3591-3596] that the experimentally observed suppression of trans -> cis isomerization yields in azobenzenes in a densely packed SAM (self-assembled monolayer) [Gahl et al., J. Am. Chem. Soc. 2010, 132, 1831-1838] is dominated by steric hindrance. In the present work, we systematically study by ground-state Langevin and nonadiabatic surface hopping dynamics, the effects of decreasing packing density on (i) UV/vis absorption spectra, (ii) trans -> cis isomerization yields, and (iii) excited-state lifetimes of photoexcited azobenzene. Within the quantum mechanics/ molecular mechanics models adopted here, we find that above a packing density of similar to 3 molecules/nm(2), switching yields are strongly reduced, while at smaller packing densities, the "monomer limit" is quickly approached. The UV/vis absorption spectra, on the other hand, depend on packing density over a larger range (down to at least similar to 1 molecule/nm(2)). Trends for excited-state lifetimes are less obvious, but it is found that lifetimes of pi pi* excited states decay monotonically with decreasing coverage. Effects of fluorination of the switches are also discussed for single, free molecules. Fluorination leads to comparatively large trans -> cis yields, in combination with long pi pi* lifetimes. Furthermore, for selected systems, also the effects of n pi* excitation at longer excitation wavelengths have been studied, which is found to enhance trans -> cis yields for free molecules but can lead to an opposite behavior in densely packed SAMs.},
  language  = {en}
}