Abstract
Time-dependent photoexcitation and optical spectroscopy of -conjugated molecules is described using a new method for the simulation of excited state molecular dynamics in extended molecular systems with sizes up to hundreds of atoms. Applications are made to poly(p-phenylene vinylene) oligomers. Our analysis shows self-trapping of excitations on about six repeat units in the course of photoexcitation relaxation, identifies specific slow (torsion) and fast (bond-stretch) nuclear motions strongly coupled to the electronic degrees of freedom, and predicts spectroscopic signatures of molecular conformations.
- Received 14 December 2001
DOI:https://doi.org/10.1103/PhysRevLett.89.097402
©2002 American Physical Society