Time-resolved photoelectron spectroscopy was used to study the energetics and dynamics of solvated electrons in aqueous solution. Solvated electrons are generated by ultrafast photodetachment in a 100 mM aqueous NaI solution. Initially, an ensemble of strongly bound ("cold") solvated electrons and an ensemble of weakly bound ("hot") electrons in an unequilibrated solvent environment are observed. We report an ultrafast recombination channel for the "hot" electrons with a rate of (800 fs)(-1) which is in competition with thermalization occurring with a rate of (1.1 ps)(-1). The thermalized electrons recombine with the iodide radical with a rate of (22 ps)(-1). About 35% of the thermalized electrons escape geminate recombination and form free, solvated electrons. The vertical detachment energy for the solvated electron is determined to be 3.40 eV. No indication for a surface-bound electron at lower binding energies was observed.

Time-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys. 2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.

Time-resolved photoelectron spectroscopy at low kinetic energies (≲5 eV) is applied to dilute iodide solutions with different surface and bulk contributions. The results indicate a pronounced surface sensitivity. Signals assigned to solvated electrons near the liquid surface decay rapidly on a sub-ps timescale. In contrast to the literature, a long-lived surface solvated electron at 1.6 eV binding energy is not observed.

Time-resolved photoelectron spectroscopy is applied to study the excited state dynamics of the DNA base adenine and its ribonucleoside adenosine in aqueous solution for pump and probe photon energies in the range between 4.66 eV and 5.21 eV. We follow the evolution of the prepared excited state on the potential energy surface and retrieve lifetimes of the S1 state under different excitation conditions.

Electrokinetic charging of aqueous microjets was characterized by measuring streaming currents as a function of sodium iodide salt concentration. Measured streaming currents at high salt concentrations (up to 0.5 M) varied nonmonotonically with the jet velocity and can be explained by a multipolar charge distribution at the nozzle-water interface. In the case of potassium fluoride no multipolar charge distribution is observed. Electrokinetic potentials were estimated from the streaming currents, under the assumption that all excess charges are confined within the liquid jet. Measured photoelectron spectra indicate much smaller streaming potentials. To resolve the apparent discrepancy, we propose that a significant fraction of excess charges evaporates in the form of ion-water clusters.