We present a model for the relaxation dynamics in perylene bisimide dimers, which is based on ab initio electronic structure and quantum dynamics calculations including effects of dissipation. The excited-state dynamics proceeds via a mixing of electronic states of local Frenkel and charge-transfer characters, which becomes effective upon a small distortion of the dimer geometry. In this way, it is possible to explain the fast depopulation of the photoexcited state, which we characterize by femtosecond transient absorption measurements. The combined theoretical and experimental analysis hints at a trapping mechanism, which involves nonadiabatic and dissipative dynamics in an excited-state vibronic manifold and provides an atomistic picture that might prove valuable for future design of photovoltaic materials.

We report calculations on high-order harmonic generation in water molecules. Spectra are determined for various initial vibrational states of H 2 O and its isotope D 2 O. It is demonstrated that the ratio of the spectra for D 2 O and H 2 O is close to unity when the initial state is the vibronic ground state, indicating that nuclear dynamics is of minor importance. For vibrationally excited initial states, the high-harmonic intensities show a clear dependence on both the initial-state quantum number and the isotopic species.

Warnericin RK is the first antimicrobial peptide known to be active against Legionella pneumophila, a pathogen bacterium that is responsible for severe pneumonia. Strikingly, this peptide displays a very narrow range of antimicrobial activity, almost limited to the Legionella genus, and a hemolytic activity. A similar activity has been described for delta-lysin, a well-known hemolytic peptide of Staphylococci that has not been described as antimicrobial. In this study we aimed to understand the mode of action of warnericin RK and to explain its particular target specificity. We found that warnericin RK permeabilizes artificial membranes in a voltage-independent manner. Osmotic protection experiments on erythrocytes showed that warnericin RK does not form well-defined pores, suggesting a detergent-like mode of action, as previously described for delta-lysin at high concentrations. Warnericin RK also permeabilized Legionella cells, and these cells displayed a high sensitivity to detergents. Depending on the detergent used, Legionella was from 10- to 1000-fold more sensitive than the other bacteria tested. Finally, the structure of warnericin RK was investigated by means of circular dichroism and NMR spectroscopy. The peptide adopted an amphiphilic alpha-helical structure, consistent with the proposed mode of action. We conclude that the specificity of warnericin RK toward Legionella results from both the detergent-like mode of action of the peptide and the high sensitivity of these bacteria to detergents.

Extending the Shin-Metiu two-electron Hamiltonian, we construct a new Hamiltonian with effective singlet-triplet couplings. The Born-Oppenheimer electronic potentials and couplings are obtained for different parameters, and the laser-free dynamics is calculated with the full Hamiltonian and in the adiabatic limit. We compare the dynamics of the system using nuclear wave packets for different numbers of Born-Oppenheimer potentials and vibronic wave packets on a full 3-dimensional (two electron coordinates plus one nuclear coordinate) grid. Using strong fields, we show that it is possible to dynamically lock the spin state of the system by decoupling the singlet-triplet transition via a nonresonant dynamic Stark effect in the adiabatic limit. Although a similar spin-locking mechanism is observed in the dynamics of vibronic wave packets, multiphoton ionization cannot be neglected leading to the breakdown of the control scheme.

We investigate pump-probe electron detachment spectroscopy in a model system which is ideally suited to study coupled electronic and nuclear wave-packet dynamics. Time-resolved photoelectron spectra are calculated within the adiabatic approximation and a discretization of the detachment continuum. These spectra are compared to those which derive from a non-Born-Oppenheimer description and a numerically exact treatment of the detachment process. In this way it is possible to identify the influence of non-adiabatic effects on the spectra in a systematic way and also to test commonly applied approximations.

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We calculate two-dimensional (2D) vibronic spectra for a model system involving two electronic molecular states. The influence of a bath is simulated using a quantum-jump approach. We use a method introduced by Makarov and Metiu [J. Chem. Phys. 111, 10126 (1999)] which includes an explicit treatment of dephasing. In this way it is possible to characterize the influence of dissipation and dephasing on the 2D-spectra, using a wave function based method. The latter scales with the number of stochastic runs and the number of system eigenstates included in the expansion of the wave-packets to be propagated with the stochastic method and provides an efficient method for the calculation of the 2D-spectra.

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