title: Coherent electronic and nuclear dynamics for charge transfer in 1-ethyl-4-(carbomethoxy)pyridinium iodide.
abstract: Although polaronic interactions and states abound in charge transfer processes and reactions, quantitative and separable determination of electronic and nuclear relaxation is still challenging. The present paper employs the amplitudes, polarizations, and phases of four-wave mixing signals to obtain unique dynamical information on relaxation processes following photoinduced charge transfer between iodide and 1-ethyl-4-(carbomethoxy)pyridinium ions. Pump-probe signal amplitudes reveal the coherent coupling of an underdamped 115 cm(-1) nuclear mode to the charge transfer excitation. Assignments of this recurrence to intramolecular vibrational modes of the acceptor and to modulation of the intermolecular donor-acceptor distance are discussed on the basis of a high-level density functional theory normal-mode analysis and previously observed wave packet dynamics of solvated molecular iodine. Nuclear relaxation of the acceptor induces sub-picosecond decay of the pump-probe polarization anisotropy from an initial value of 0.4 to an asymptotic value of -0.05. Electronic structure calculations suggest that relaxation along the torsional coordinate of the ethyl group is the origin of the anisotropy decay. Electric-field-resolved transient grating (EFR-TG) signal fields are obtained by spectral interferometry with a diffractive optic based interferometer. These measurements show that the signal phase and amplitude possess similar dynamics. Model calculations are used to demonstrate how the EFR-TG signal phase yields unique information on transient material resonances located outside the laser pulse spectrum. This effect can be rationalized in that the real and imaginary parts of the nonlinear polarization are related by the Kramers-Kronig transformation, which allows the dispersive component of the polarization response to exhibit spectral sensitivity over a larger frequency range than that defined by the absorption bandwidth.
authors.affiliation: Department of Chemistry and the James Franck Institute, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, USA.
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Moran
authors.forename: Sungnam
authors.initials: S
authors.lastname: Park
authors.forename: Norbert F
authors.initials: NF
authors.lastname: Scherer
mesh_terms: D000465:Algorithms; D016880:Anisotropy; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D004553:Electric Conductivity; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D007454:Iodides / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008958:Models, Molecular; D017785:Photons; D011726:Pyridinium Compounds / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods; D055672:Static Electricity
chemical_list: D005609:Free Radicals; D007454:Iodides; D007477:Ions; D011726:Pyridinium Compounds; D012997:Solvents; C011815:ethylpyridinium