title: Quasiperiodic energy dependence of exciton relaxation kinetics in the sexithiophene crystal.
abstract: Femtosecond kinetics of fluorescence rise in the sexithiophene crystal is studied on a microscopic model of intraband relaxation, where exciton energy is assumed to be dissipated by phonon-accompanied scattering, with the rates calculated earlier. The temporal evolution of the exciton population is described by a set of kinetic equations, solved numerically to yield the population buildup at the band bottom. Not only the time scale but also the shape of the rise curves is found to be unusually sensitive to excitation energy, exhibiting unique quasiperiodic dependence thereon, which is rationalized in terms of the underlying model. Further simulations demonstrate that the main conclusions are robust with respect to experimental factors such as finite temperature and inherent spectral broadening of the exciting pulse, while the calculated fluorescence rise times are found to be in excellent agreement with experimental data available to date. As the rise profiles are composed of a number of exponential contributions, which varies with excitation energy, the common practice of characterizing the population buildup in the emitting state by a single value of relaxation time turns out to be an oversimplification. New experiments giving further insight into the kinetics and mechanism of intraband exciton relaxation are suggested.
authors.affiliation: K. Gumiński Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University , ul. Ingardena 3, 30-060 Krakow, Poland.
authors.forename: Piotr
authors.initials: P
authors.lastname: Petelenz
authors.forename: Emil
authors.initials: E
authors.lastname: Zak
mesh_terms: D003198:Computer Simulation; D005453:Fluorescence; D006576:Heterocyclic Compounds, 4 or More Rings / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D060739:Phonons; D012542:Scattering, Radiation; D013696:Temperature; D013876:Thiophenes / Q000737:chemistry*
chemical_list: D006576:Heterocyclic Compounds, 4 or More Rings; D013876:Thiophenes; C520246:sexithiophene