@article{ObergGladhAnniyevetal.2015,
  author    = {Oberg, H. and Gladh, J{\"o}rgen and Anniyev, Toyli and Beye, Martin and Coffee, Ryan and F{\"o}hlisch, Alexander and Katayama, T. and Kaya, Sarp and LaRue, Jerry and Mogelhoj, Andreas and Nordlund, Dennis and Ogasawara, Hirohito and Schlotter, William F. and Sellberg, Jonas A. and Sorgenfrei, Florian and Turner, Joshua J. and Wolf, Martin and Wurth, W. and Ostrom, Henrik and Nilsson, Anders and Norskov, Jens K. and Pettersson, Lars G. M.},
  title     = {Optical laser-induced CO desorption from Ru(0001) monitored with a free-electron X-ray laser: DFT prediction and X-ray confirmation of a precursor state},
  series = {Surface science},
  volume    = {640},
  journal   = {Surface science},
  publisher = {Elsevier},
  address   = {Amsterdam},
  issn      = {0039-6028},
  doi       = {10.1016/j.susc.2015.03.011},
  pages     = {80 -- 88},
  year      = {2015},
  abstract  = {We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (<100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of similar to 2000K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (similar to 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate. (C) 2015 Elsevier B.V. All rights reserved.},
  language  = {en}
}
@article{KroenerGoetze2012,
  author    = {Kr{\"o}ner, Dominik and G{\"o}tze, Jan Philipp},
  title     = {Modeling of a violaxanthin-chlorophyll b chromophore pair in its LHCII environment using CAM-B3LYP},
  series = {Journal of photochemistry and photobiology : B, Biology},
  volume    = {109},
  journal   = {Journal of photochemistry and photobiology : B, Biology},
  number    = {2},
  publisher = {Elsevier},
  address   = {Lausanne},
  issn      = {1011-1344},
  doi       = {10.1016/j.jphotobiol.2011.12.007},
  pages     = {12 -- 19},
  year      = {2012},
  abstract  = {Collecting energy for photosystem II is facilitated by several pigments, xanthophylls and chlorophylls, embedded in the light harvesting complex II (LHCII). One xanthophyll, violaxanthin (Vio), is loosely bound at a site close to a chlorophyll b (Chl). No final answer has yet been found for the role of this specific xanthophyll. We study the electronic structure of Vio in the presence of Chl and under the influence of the LHCII environment, represented by a point charge field (PCF). We compare the capability of the long range corrected density functional theory (DFT) functional CAM-B3LYP to B3LYP for the modeling of the UV/vis spectrum of the Vio + Chl pair. CAM-B3LYP was reported to allow for a very realistic reproduction of bond length alternation of linear polyenes, which has considerable impact on the carotenoid structure and spectrum. To account for the influence of the LHCII environment, the chromophore geometries are optimized using an ONIOM(DFT/6-31G(d):PM6) scheme. Our calculations show that the energies of the locally excited states are almost unaffected by the presence of the partner chromophore or the PCF. There are, however, indications for excitonic coupling of the Chl Soret band and Vio. We propose that Vio may accept energy from blue-light excited Chl.},
  language  = {en}
}