Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 118, Issue 45, Pages 10372-10379Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp503350k
Keywords
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Funding
- CONICET
- UNQ
- ANPCyT [PICT-2010-2375]
- National Science Foundation [CHE-0239129, CHE-0808910]
- U.S. Department of Energy
- Los Alamos LDRD
- National Nuclear Security Administration of the U.S. Department of Energy [DE-AC5206NA25396]
- Center for Integrated Nanotechnologies (CINT)
- Center for Nonlinear Studies (CNLS) at LANL
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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.
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