Signature of nonadiabatic coupling in excited-state vibrational modes.
Using analytical excited-state gradients, vibrational normal modes have been calculated at the minimum of the electronic excited-state potential energy surfaces for a set of extended conjugated molecules with different coupling between them. Molecular model systems composed of units of polyphenylene ethynylene (PPE), polyphenylenevinylene (PPV), and naphthacene/pentacene (NP) have been considered. In all cases except the NP model, the influence of the nonadiabatic coupling on the excited-state equilibrium normal modes is revealed as a unique highest frequency adiabatic vibrational mode that overlaps with the coupling vector. This feature is removed by using a locally diabatic representation in which the effect of NA interaction is removed. Comparison of the original adiabatic modes with a set of vibrational modes computed in the locally diabatic representation demonstrates that the effect of nonadiabaticity is confined to only a few modes. This suggests that the nonadiabatic character of a molecular system may be detected spectroscopically by identifying these unique state-specific high frequency vibrational modes.
Universidad Nacional de Quilmes , Roque Saenz Peña 352, B1876BXD Bernal, Argentina.
Miguel A
MA
Soler
Tammie
T
Nelson
Adrian E
AE
Roitberg
Sergei
S
Tretiak
Sebastian
S
Fernandez-Alberti
D000465:Algorithms; D008958:Models, Molecular; D009279:Naphthacenes / Q000737:chemistry; D011108:Polymers / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods*; D014732:Vibration
D009279:Naphthacenes; D011108:Polymers; C473966:poly(phenylene ethynylene); C523499:pentacene; C487736:naphthacene