The temperature dependence of radiationless transition rates from ab initio computations

Raffaele Borrelli, Andrea Peluso
2011 Physical Chemistry, Chemical Physics - PCCP  
The temperature dependence of radiationless transition rates from ab initio computations / R. Abstract The calculation of radiationless transition rates and of their temperature dependence from first principles is addressed by combining reliable electronic computations of the normal modes of the two electronic states with Kubo's generating function approach for the evaluation of the Franck-Condon weighted density of states. The whole sets of normal modes of the involved cofactors have been
more » ... tors have been employed, taking into account the effects of nuclear equilibrium position displacements, of vibrational frequency changes, and of mixing of the normal modes. Application to the case of the elementary electron transfer step between bacteriopheophytin and ubiquinone cofactors of bacterial photosynthetic reaction centers yields a temperature dependence of the electron transfer rates in very good agreement with the experimental data.
doi:10.1039/c0cp02307h pmid:21258672 fatcat:ruz4l53lgndqxk4dgt3bperuse