@article{GoetzeSaalfrank2012,
  author    = {G{\"o}tze, Jan Philipp and Saalfrank, Peter},
  title     = {Quantum chemical modeling of the kinetic isotope effect of the carboxylation step in RuBisCO},
  series = {Journal of molecular modeling},
  volume    = {18},
  journal   = {Journal of molecular modeling},
  number    = {5},
  publisher = {Springer},
  address   = {New York},
  issn      = {1610-2940},
  doi       = {10.1007/s00894-011-1207-0},
  pages     = {1877 -- 1883},
  year      = {2012},
  abstract  = {Ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO), the most important enzyme for the assimilation of carbon into biomass, features a well-known isotope effect with regards to the CO2 carbon atom. This kinetic isotope effect alpha = k (12)/k (13) for the carboxylation step of the RuBisCO reaction sequence, and its microscopic origin, was investigated with the help of cluster models and quantum chemical methods [B3LYP/6-31G(d,p)]. We use a recently proposed model for the RuBisCO active site, in which a water molecule remains close to the reaction center during carboxylation of ribulose-1,5-bisphosphate [B. Kannappan, J.E. Gready, J. Am. Chem. Soc. 130 (2008), 15063]. Alternative active-site models and/or computational approaches were also tested. An isotope effect alpha for carboxylation is found, which is reasonably close to the one measured for the overall reaction, and which originates from a simple frequency shift of the bending vibration of (CO2)-C-12 compared to (CO2)-C-13. The latter is the dominant mode for the product formation at the transition state.},
  language  = {en}
}