We have performed ultrafast three-dimensional ion momentum imaging spectroscopy on the dissociative single ionization of oxygen molecules using attosecond pulse trains with a broad energy spectrum of 5-30 eV. High-resolution momentum imaging allows clear identification of vibrational structures corresponding to the predissociation of highly excited cationic states. By adding a pump infrared field that is synchronized with and polarized orthogonally to the XUV pulse train, and an additional probe IR field, we demonstrate how the yield of O+ ions can be steered between different dissociation channels by coherently controlling the coupling between multiple O-2(+*) electronic states on an attosecond time scale. Time-dependent calculations in a single active electron approximation allow a qualitative analysis of ion yields for two orientations of the molecular axis.

We used ultrashort femtosecond vacuum ultraviolet (VUV) and infrared (IR) pulses in a pump-probe scheme to map the dynamics and nonequilibrium dissociation channels of excited neutral ${\text{H}}_{2}$ molecules. A nuclear wave packet is created in the $B\phantom{\rule{0.16em}{0ex}}^{1}\mathrm{\ensuremath{\Sigma}}_{u}^{+}$ state of the neutral ${\text{H}}_{2}$ molecule by absorption of the ninth harmonic of the driving infrared laser field. Due to the large stretching amplitude of the molecule excited in the $B\phantom{\rule{0.16em}{0ex}}^{1}\mathrm{\ensuremath{\Sigma}}_{u}^{+}$ electronic state, the effective ${\text{H}}_{2}{}^{+}$ ionization potential changes significantly as the nuclear wave packet vibrates in the bound, highly electronically and vibrationally excited $B$ potential-energy curve. We probed such dynamics by ionizing the excited neutral molecule using time-delayed VUV-or-IR radiation. We identified the nonequilibrium dissociation channels by utilizing three-dimensional momentum imaging of the ion fragments. We found that different dissociation channels can be controlled, to some extent, by changing the IR laser intensity and by choosing the wavelength of the probe laser light. Furthermore, we concluded that even in a benchmark molecular system such as ${\text{H}}_{2}$*, the interpretation of the nonequilibrium multiphoton and multicolor ionization processes is still a challenging task, requiring intricate theoretical analysis.

We present a study of the ultrafast dissociation dynamics of the lowest-lying electronic excited states in CO2 by using ultraviolet (UV) and extreme-ultraviolet (XUV) pulses from high-order harmonic generation. We observe two primary dissociation channels: a direct dissociation channel along the (1)Pi(g) electronically excited manifold, and a second channel which results from the mixing of electronic states. The direct dissociation channel is found to have a lifetime which is shorter than our experimental resolution, whereas the second channel has a significantly longer lifetime of nearly 200 fs. In this long-lived channel we observe a beating of the vibrational populations with a period of similar to 133 fs.

We present a measurement of the time-resolved photoelectron kinetic energy spectrum of ethylene using 156 nm and 260 nm laser pulses. The 156 nm pulse first excites ethylene to the (1)B1u (ππ(∗)) electronic state where 260 nm light photoionizes the system to probe the relaxation dynamics with sub-30 fs resolution. Recent ab initio calculations by Mori et al. [J. Phys. Chem. A 116, 2808-2818 (2012)] have predicted an ultrafast population transfer from the initially excited state to a low-lying Rydberg state during the relaxation of photoexcited ethylene. The measured photoelectron kinetic energy spectrum reveals wave packet motion on the valence state and shows indications that the low-lying π3s Rydberg state is indeed transiently populated via internal conversion following excitation to the ππ(∗) state, supporting the theoretical predictions.

Using signal onset times, time-resolved photoelectron kinetic energy spectra from a two VUV photon pump-probe scheme allow for the tracking of ultrafast (<10 fs) non-adiabatic dynamics of valence excited molecules.

We report the reflectance, ~1° from normal incidence, of six different mirrors as a function of photon energy, using monochromatic vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) radiation with energies between 7.5 eV and 24.5 eV. The mirrors examined included both single and multilayer optical coatings, as well as an uncoated substrate. We discuss the performance of each mirror, paying particular attention to the potential application of suppression and selection of high-order harmonics of a Ti:sapphire laser.

Submitted for the DAMOP16 Meeting of The American Physical Society Attosecond Coherent Control of the Photo-Dissociation of Oxygen Molecules1 FELIX STURM, DIPANWITA RAY, TRAVIS WRIGHT, NIRANJAN SHIVARAM, IRINA BOCHAROVA, DANIEL SLAUGHTER, Lawrence Berkeley National Lab, PREDRAG RANITOVIC, Extreme Light Infrastructure, ALI BELKACEM, THORSTEN WEBER, Lawrence Berkeley National Lab — Attosecond Coherent Control has emerged in recent years as a technique to manipulate the absorption and ionization in atoms as well as the dissociation of molecules on an attosecond time scale. Single attosecond pulses and attosecond pulse trains (APTs) can coherently excite multiple electronic states. The electronic and nuclear wave packets can then be coupled with a second pulse forming multiple interfering quantum pathways. We have built a high flux extreme ultraviolet (XUV) light source delivering APTs based on HHG that allows to selectively excite neutral and ion states in molecules. Our beamline provides spectral selectivity and attosecond interferometric control of the pulses. In the study presented here, we use APTs, generated by High Harmonic Generation in a high flux extreme ultraviolet light source, to ionize highly excited states of oxygen molecules. We identify the ionization/dissociation pathways revealing vibrational structure with ultra-high resolution ion 3D-momentum imaging spectroscopy. Furthermore, we introduce a delay between IR pulses and XUV/IR pulses to constructively or destructively interfere the ionization and dissociation pathways, thus, enabling the manipulation of both the O2 and the O + ion yields with attosecond precision. 1supported by DOE under Contract No. DE-AC02-05CH11231 Thorsten Weber Lawrence Berkeley National Lab Date submitted: 01 Mar 2016 Electronic form version 1.4

We demonstrate a technique in velocity map imaging (VMI) that allows spatial gating of the laser focal overlap region in time resolved pump-probe experiments. This significantly enhances signal-to-noise ratio by eliminating background signal arising outside the region of spatial overlap of pump and probe beams. This enhancement is achieved by tilting the laser beams with respect to the surface of the VMI electrodes which creates a gradient in flight time for particles born at different points along the beam. By suitably pulsing our microchannel plate detector, we can select particles born only where the laser beams overlap. This spatial gating in velocity map imaging can benefit nearly all photo-ion pump-probe VMI experiments especially when extreme-ultraviolet light or X-rays are involved which produce large background signals on their own.

We present a new experimental setup for measuring ultrafast nuclear and electron dynamics of molecules after photo-excitation and ionization. We combine a high flux femtosecond vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) source with an internally cold molecular beam and a 3D momentum imaging particle spectrometer to measure electrons and ions in coincidence. We describe a variety of tools developed to perform pump-probe studies in the VUV-XUV spectrum and to modify and characterize the photon beam. First benchmark experiments are presented to demonstrate the capabilities of the system.