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.

Using femtosecond time-resolved x-ray diffraction, we directly monitor the coherent lattice dynamics through an ultrafast charge-density-wave-to-metal transition in the prototypical Peierls system K(0.3)MoO(3) over a wide range of relevant excitation fluences. While in the low fluence regime we directly follow the structural dynamics associated with the collective amplitude mode; for fluences above the melting threshold of the electronic density modulation we observe a transient recovery of the periodic lattice distortion. We can describe these structural dynamics as a motion along the coordinate of the Peierls distortion triggered by the prompt collapse of electronic order after photoexcitation. The results indicate that the dynamics of a structural symmetry-breaking transition are determined by a high-symmetry excited state potential energy surface distinct from that of the initial low-temperature state.

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 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.

Femtosecond time-resolved X-ray diffraction is used to study a photo-induced phase transition between two charge density wave (CDW) states in 1T-TaS2, namely the nearly commensurate (NC) and the incommensurate (I) CDW states. Structural modulations associated with the NC-CDW order are found to disappear within 400 fs. The photo-induced I-CDW phase then develops through a nucleation/growth process which ends 100 ps after laser excitation. We demonstrate that the newly formed I-CDW phase is fragmented into several nanometric domains that are growing through a coarsening process. The coarsening dynamics is found to follow the universal Lifshitz-Allen-Cahn growth law, which describes the ordering kinetics in systems exhibiting a non-conservative order parameter.Among strongly correlated electron systems, superconductors and materials exhibiting metal-insulator transitions are usually characterized by strong electronelectron and electron-phonon couplings [1][2][3]. At thermodynamic equilibrium, the corresponding many-body interactions lead to rich phase diagrams as a function of temperature, pressure or doping. Such compounds also display fascinating out-of-equilibrium physics, in the form of ultra-fast symmetry changes known as photoinduced phase transitions [4][5][6], and occurrence of new, transient states [6][7][8].Charge density wave (CDW) states are broken symmetry states of metals arising from electron-phonon interactions. They are characterized by a periodic modulation of both atomic positions and electron density. The metal-to-CDW phase transition is characterized by the growth of a complex-valued order parameter p = A exp iΦ , which reflects both the amplitude A and the phase Φ of the periodic modulation [3]. A number of photo-induced phase transitions that have been achieved in CDW compounds correspond to a suppression of the CDW order, i.e. a transition between a CDW state and a metallic state free of any structural modulation [5,[9][10][11][12][13][14][15]. Among those, the photo-induced suppression of the CDW state in blue bronze was shown to involve a coherent motion of atoms along the normal coordinates of the CDW amplitude mode [5]. In this case, the amplitude mode allows continuous variations of the modulus of the order parameter |p|, the metallic state corresponding to |p|=0. In the present work, we focus on the photo-induced phase transition between the nearly commensurate (NC) and the incommensurate (I) CDW states in 1T-TaS 2 , which exhibit two distinct order parameters. When thermallyinduced, this first-order phase transition involves a discontinuous change of atomic positions, and a coexistence of NC and I phase domains over a 3 K range [16,17]. It is thus expected that the photo-induced I phase appears through non-coherent atomic motions, by a nucleation/growth process. We report that the photo-induced NC → I phase is completed within 100 ps after laser excitation. At this 100 ps delay, the photo-induced I-CDW phase is found divided into domains with a typical size of 150Å. Its ordering kinet...

Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter’s dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti3+ centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides.

The displacive phase transition in SrTiO3 was investigated by means of x-ray diffraction. We used 4.5 keV photons thus probing only a very thin region near the surface. In the low temperature phase the lattice parameters evolve substantially different than in bulk material. We also investigated the phase transition under the influence of an epitaxial coating with YBaCu2O7 and found the nature of the phase transition changed. The near-surface region behaves like an epitaxial thin SrTiO3 film.

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.