Vibrational effects in laser driven molecular wires

The influence of an electron-vibrational coupling on the laser control of electron transport through a molecular wire that is attached to several electronic leads is investigated. These molecular vibrational modes induce an effective electron-electron interaction. In the regime where the wire electrons couple weakly to both the external leads and the vibrational modes, we derive within a Hartree-Fock approximation a nonlinear set of quantum kinetic equations. The quantum kinetic theory is then used to evaluate the laser driven, time-averaged electron current through the wire-leads contacts. This novel formalism is applied to two archetypical situations in the presence of electron-vibrational effects, namely, (i) the generation of a ratchet or pump current in a symmetrical molecule by a harmonic mixing field and (ii) the laser switching of the current through the molecule.Comment: 12 pages, 7 figures, RevTeX4 require

Ultrafast heterogeneous electron transfer reactions Comparative theoretical studies on time and frequency domain data

Recent theoretical studies on linear absorption spectra of dye semiconductor systems perylene attached to nanostructured TiO2, L. Wang et al., J. Phys. Chem. B 109, 9589 2005 are extended here in different respects. Since the systems show ultrafast photoinduced heterogeneous electron transfer the time dependent formulation used to compute the absorbance is also applied to calculate the temporal evolution of the sub 100 fs charge injection dynamics after a 10 fs laser pulse excitation. These studies complement our recent absorption spectra fit for two perylene bridge anchor group TiO2 systems. Moreover, the time dependent formulation of the absorbance is confronted with a frequency domain description. The latter underlines the central importance of the self energy caused by the coupling of the dye levels to the semiconductor band continuum. The used model is further applied to study the effect of different parameters such as 1 the dependence on the reorganization energies of the involved intramolecular transitions, 2 the effect of changing the transfer integral which couples the excited dye state with the band continuum, and 3 the effect of the concrete form of the semiconductor band density of states. Emphasis is also put on the case where the charge injection level of the dye is near or somewhat below the band edge. This nicely demonstrates the change from a structureless absorption to a well resolved vibrational progression including characteristic shifts of the absorption lines which are a direct measure for the dye semiconductor couplin

Charge and Energy Transfer Dynamics in Molecular Systems

This 3rd edition has been expanded and updated to account for recent developments, while new illustrative examples as well as an enlarged reference list have also been added. It naturally retains the successful concept of its predecessors in presenting a unified perspective on molecular charge and energy transfer processes, thus bridging the regimes of coherent and dissipative dynamics, and establishing a connection between classic rate theories and modern treatments of ultrafast phenomena. Among the new topics are:Time-dependent density functional theoryHeterogeneous electron transfer, e.g.