A full-dimensional Franck-Condon calculation has been applied to the à (1)Au-X̃ 1Σg+ transition in acetylene in the harmonic normal mode basis. Details of the calculation are discussed in Part I of this series. To our knowledge, this is the first full-dimensional Franck-Condon calculation on a tetra-atomic molecule undergoing a linear-to-bent geometry change. In the current work, the vibrational...

A strong enhancement of absorption to the lowest A1 state is observed for vibrationally excited chloromethyl radicals. It is demonstrated that this enhancement is due to a significant increase in both electronic and vibrational Franck–Condon factors. Electronic structure calculations of potential energy surfaces ~PESs! and transition dipole moments for the ground and the two lowest excited stat...

Fabio Cavaliere,1 Eros Mariani,2,3 Renaud Leturcq,4,5 Christoph Stampfer,4,6 and Maura Sassetti1 1CNR-SPIN and Dipartimento di Fisica, Università di Genova, Via Dodecaneso 33, 16146 Genova, Italy 2Institut für Theoretische Physik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, Germany 3School of Physics, University of Exeter, Stocker Road, Exeter EX4 4QL, United Kingdom 4Laboratory for ...

Excited-state relaxations in molecules are responsible for a red shift of the absorption peak with respect to the emission peak (Franck-Condon shift). The magnitude of this shift in semiconductor quantum dots is still unknown. Here we report first-principle calculations of excited-state relaxations in small (diameter ≤ 2.2 nm) Si nanocrystals, showing that the Franck-Condon shift is surprisingl...

Franck-Condon effects associated with intervalence excitation of the Creutz-Taube ion (a prototypical delocalized mixed-valency system) have been evaluated via a time-dependent analysis of resonance Raman scattering intensities and the intervalence absorption lineshape. Quantitative studies in the extended near infrared (1320 nm excitation) revealed that at least eight, and possibly nine, vibra...