Preface to the Third Edition XIII Preface to the Second Edition XV Preface to the First Edition XVII 1 Introduction 1 2 Electronic and Vibrational Molecular States 9 2.1 Introduction 9 2.2 Molecular Schrödinger Equation 11 2.3 Born-Oppenheimer Separation 13 2.3.1 Born-Oppenheimer Approximation 15 2.3.2 Some Estimates 17 2.4 Electronic Structure Methods 18 2.4.1 The Hartree-Fock Equations 21 2.4.2 Density Functional Theory 23 2.5 Condensed Phase Approaches 24 2.5,1 Dielectric Continuum Model 25 2.5.2 Explicit Quantum-Classical Solvent Model 31 2.6

Preface to the Third Edition XIII Preface to the Second Edition XV Preface to the First Edition XVII 1 Introduction 1 2 Electronic and Vibrational Molecular States 9 2.1 Introduction 9 2.2 Molecular Schrödinger Equation 11 2.3 Born-Oppenheimer Separation 13 2.3.1 Born-Oppenheimer Approximation 15 2.3.2 Some Estimates 17 2.4 Electronic Structure Methods 18 2.4.1 The Hartree-Fock Equations 21 2.4.2 Density Functional Theory 23 2.5 Condensed Phase Approaches 24 2.5,1 Dielectric Continuum Model 25 2.5.2 Explicit Quantum-Classical Solvent Model 31 2.6

No abstract

Linear absorption spectra of dye-semiconductor systems (perylene attached to nanostructured TiO2) are studied theoretically and experimentally. The systems show ultrafast photoinduced heterogeneous electron transfer (HET). By applying a time-dependent formulation of the absorbance, the theoretical analysis of the measured data is carried out. The respective electron-vibrational wave packet propagation fully accounts for the electronic coupling to the conduction band continuum of TiO2 and is based on a single-reaction-coordinate model (corresponding to a perylene in-plane C-C stretching vibration with a quantum energy of 1370 cm(-1)). By the insertion of different bridge-anchor groups, the electronic coupling responsible for HET is varied. The dye absorbance in a solvent and the trends in the line broadening of the vibrational progression due to the coupling to the conduction band continuum are reproduced for all investigated types of bridge-anchor groups. HET rates deduced from the calculations on the absorbance displaying line broadenings follow the qualitative trend obtained from transient absorption spectra.

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 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.