ABSTRACT
Free electrons in a polar liquid can form a bound state via interaction with the molecular environment. This so-called hydrated electron state in water is of fundamental importance, e.g., in cellular biology or radiation chemistry. Hydrated electrons are highly reactive radicals that can either directly interact with DNA or enzymes, or form highly excited hydrogen (H^{*}) after being captured by protons. Here, we investigate the formation of the hydrated electron in real-time employing extreme ultraviolet femtosecond pulses from a free electron laser, in this way observing the initial steps of the hydration process. Using time-resolved photoelectron spectroscopy we find formation timescales in the low picosecond range and resolve the prominent dynamics of forming excited hydrogen states.
ABSTRACT
Time-resolved photoelectron spectroscopy (TRPES) is a useful approach to elucidate the coupled electronic-nuclear quantum dynamics underlying chemical processes, but has remained limited by the use of low photon energies. Here, we demonstrate the general advantages of XUV-TRPES through an application to NO2, one of the simplest species displaying the complexity of a non-adiabatic photochemical process. The high photon energy enables ionization from the entire geometrical configuration space, giving access to the true dynamics of the system. Specifically, the technique reveals dynamics through a conical intersection, large-amplitude motion and photodissociation in the electronic ground state. XUV-TRPES simultaneously projects the excited-state wave packet onto many final states, offering a multi-dimensional view of the coupled electronic and nuclear dynamics. Our interpretations are supported by ab initio wavepacket calculations on new global potential-energy surfaces. The presented results contribute to establish XUV-TRPES as a powerful technique providing a complete picture of ultrafast chemical dynamics from photoexcitation to the final products.
ABSTRACT
We present a new design of a time-preserving extreme-ultraviolet (XUV) monochromator using a semi-infinite gas cell as a source. The performance of this beamline in the photon-energy range of 20 eV-42 eV has been characterized. We have measured the order-dependent XUV pulse durations as well as the flux and the spectral contrast. XUV pulse durations of ≤40 fs using 32 fs, 800 nm driving pulses were measured on the target. The spectral contrast was better than 100 over the entire energy range. A simple model based on the strong-field approximation is presented to estimate different contributions to the measured XUV pulse duration. On-axis phase-matching calculations are used to rationalize the variation of the photon flux with pressure and intensity.
