@article{BuechnerdaCruzGroveretal.2022,
  author    = {B{\"u}chner, Robby and da Cruz, Vinicius Vaz and Grover, Nitika and Charisiadis, Asterios and Fondell, Mattis and Haverkamp, Robert and Senge, Mathias O. and F{\"o}hlisch, Alexander},
  title     = {Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin},
  series = {Physical chemistry, chemical physics : a journal of European Chemical Societies},
  volume    = {24},
  journal   = {Physical chemistry, chemical physics : a journal of European Chemical Societies},
  number    = {12},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1463-9076},
  doi       = {10.1039/d1cp05420a},
  pages     = {7505 -- 7511},
  year      = {2022},
  abstract  = {Free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin stands for the class of powerful porphyrin photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy in combination with time-dependent density functional theory (TD-DFT) gives direct access to the crucial excited molecular states within the unusual relaxation pathway. The efficient intersystem crossing, that is El-Sayed forbidden and not facilitated by a heavy atom is confirmed to be the result of the long singlet excited state lifetime (Q(x) 4.9 ns) and thermal effects. Overall, the interplay of stabilization by conservation of angular momenta and vibronic relaxation drive the de-excitation in these chromophores.},
  language  = {en}
}