J. van Tilborg

Ultrafast internal conversion in ethylene. I. The excited state lifetime

Using a combined theoretical and experimental approach, we investigate the non-adiabatic dynamics of the prototypical ethylene (C(2)H(4)) molecule upon π → π∗ excitation. In this first part of a two part series, we focus on the lifetime of the excited electronic state. The femtosecond time-resolved photoelectron spectrum (TRPES) of ethylene is simulated based on our recent molecular dynamics simulation using the ab initio multiple spawning method with multi-state second order perturbation theory [H. Tao, B. G. Levine, and T. J. Martinez, J. Phys. Chem. A 113, 13656 (2009)]. We find excellent agreement between the TRPES calculation and the photoion signal observed in a pump-probe experiment using femtosecond vacuum ultraviolet (hν = 7.7 eV) pulses for both pump and probe. These results explain the apparent discrepancy over the excited state lifetime between theory and experiment that has existed for ten years, with experiments [e.g., P. Farmanara, V. Stert, and W. Radloff, Chem. Phys. Lett. 288, 518 (1998) and K. Kosma, S. A. Trushin, W. Fuss, and W. E. Schmid, J. Phys. Chem. A 112, 7514 (2008)] reporting much shorter lifetimes than predicted by theory. Investigation of the TRPES indicates that the fast decay of the photoion yield originates from both energetic and electronic factors, with the energetic factor playing a larger role in shaping the signal.

Active Plasma Lensing for Relativistic Laser-Plasma-Accelerated Electron Beams

Compact, tunable, radially symmetric focusing of electrons is critical to laser-plasma accelerator (LPA) applications. Experiments are presented demonstrating the use of a discharge-capillary active plasma lens to focus 100-MeV-level LPA beams. The lens can provide tunable field gradients in excess of 3000 T/m, enabling cm-scale focal lengths for GeV-level beam energies and allowing LPA-based electron beams and light sources to maintain their compact footprint. For a range of lens strengths, excellent agreement with simulation was obtained.

Frequency chirp and pulse shape effects in self-modulated laser wakefield accelerators

The effect of asymmetric laser pulses on plasma wave excitation in a self-modulated laser wakefield accelerator is examined. Laser pulse shape and frequency chirp asymmetries, controlled experimentally in the laser system through a grating pair compressor, are shown to strongly enhance measured electron yields for certain asymmetries. It is shown analytically that a positive (negative) frequency chirp enhances (suppresses) the growth rate of the Raman forward scattering and near-forward Raman sidescatter instabilities, but is of minimal importance for the experimental parameters. Temporal laser pulse shapes with fast rise times (≲ plasma period) are shown to generate larger wakes (compared to slow rise time pulses) which seed the growth of the plasma wave, resulting in enhanced electron yield.

Ultrafast internal conversion in ethylene. II. Mechanisms and pathways for quenching and hydrogen elimination

Through a combined experimental and theoretical approach, we study the nonadiabatic dynamics of the prototypical ethylene (C(2)H(4)) molecule upon π → π(∗) excitation with 161 nm light. Using a novel experimental apparatus, we combine femtosecond pulses of vacuum ultraviolet and extreme ultraviolet (XUV) radiation with variable delay to perform time resolved photo-ion fragment spectroscopy. In this second part of a two part series, the XUV (17 eV < hν < 23 eV) probe pulses are sufficiently energetic to break the C-C bond in photoionization, or to photoionize the dissociation products of the vibrationally hot ground state. The experimental data is directly compared to excited state ab initio molecular dynamics simulations explicitly accounting for the probe step. Enhancements of the CH(2)(+) and CH(3)(+) photo-ion fragment yields, corresponding to molecules photoionized in ethylene (CH(2)CH(2)) and ethylidene (CH(3)CH) like geometries are observed within 100 fs after π → π(∗) excitation. Quantitative agreement between theory and experiment on the relative CH(2)(+) and CH(3)(+) yields provides experimental confirmation of the theoretical prediction of two distinct conical intersections and their branching ratio [H. Tao, B. G. Levine, and T. J. Martinez, J. Phys. Chem. A. 113, 13656 (2009)]. Evidence for fast, non-statistical, elimination of H(2) molecules and H atoms is observed in the time resolved H(2)(+) and H(+) signals.

Generation and pointing stabilization of multi-GeV electron beams from a laser plasma accelerator driven in a pre-formed plasma waveguidea)

Laser pulses with peak power 0.3 PW were used to generate electron beams with energy >4 GeV within a 9 cm-long capillary discharge waveguide operated with a plasma density of ≈7×1017 cm−3. Simulations showed that the super-Gaussian near-field laser profile that is typical of high-power femtosecond laser systems reduces the efficacy of guiding in parabolic plasma channels compared with the Gaussian laser pulses that are typically simulated. In the experiments, this was mitigated by increasing the plasma density and hence the contribution of self-guiding. This allowed for the generation of multi-GeV electron beams, but these had angular fluctuation ≳2 mrad rms. Mitigation of capillary damage and more accurate alignment allowed for stable beams to be produced with energy 2.7±0.1 GeV. The pointing fluctuation was 0.6 mrad rms, which was less than the beam divergence of ≲1 mrad full-width-half-maximum.

Single-shot spatiotemporal measurements of ultrashort THz waveforms using temporal electric-field cross correlation

A new single-shot technique based on linear spectral interferometry between a temporally short reader pulse and a temporally long probe pulse is demonstrated for measuring the spatiotemporal phase and amplitude of an optical probe for use as an ultrafast diagnostic. The probe spatiotemporal field information is recovered, with a resolution set by the duration of the reader pulse, by applying a single Fourier transform operation to the interferogram image, without need of any reference data. The technique was used in conjunction with electro-optic sampling to measure waveforms of coherent, ultrashort THz pulses emitted by electron bunches from a laser-plasma accelerator with sub-50fs resolution. The presence of strong spatiotemporal coupling in the THz waveforms and of complex temporal electron-bunch structure was determined.

Femtosecond isomerization dynamics in the ethylene cation measured in an EUV-pump NIR-probe configuration

FAST TRACK COMMUNICATION Femtosecond isomerization dynamics in the ethylene cation measured in an EUV-pump NIR-probe configuration J. van Tilborg 1 , T. K. Allison 1,2 , T. W. Wright 1 , M. P. Hertlein 1 , R. W. Falcone 1,2 , Y. Liu 1 , H. Merdji 3 , A. Belkacem 1 Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA University of California at Berkeley, Berkeley, California 94720, USA Service des Photons, Atomes et Mol´ cules, CEA-Saclay, 91191 Gif-sur-Yvette, e France E-mail: JvanTilborg@lbl.gov Abstract. Dynamics in the excited ethylene cation C 2 H + lead to isomerization to the ethylidene configuration (HC-CH 3 ) + , which is predicted to be a transient configuration for electronic relaxation. With an intense femtosecond EUV (extreme ultraviolet) pump pulse to populate the excited state, and an NIR (near infrared) probe pulse to produce the fragments CH + and CH + (which provides a direct signature of ethylidene), we measure optimum fragment yields at a probe delay of 80 fs. Also, an H 2 -stretch transient configuration, yielding H + upon probing, is found to succeed the ethylidene configuration. We find that a simple single- or double-decay model does not match the data, and we present a modified model (introduction of an isomerization delay of 50 ± 25 fs) that does provide agreement. PACS numbers: 33.80.-b, 33.80.Rv, 33.50.Hv, 31.50.-x

Tuning of laser pulse shapes in grating-based compressors for optimal electron acceleration in plasmas

The temporal shape (rise time, fall time, skewness) of 50-200-fs Ti:sapphire laser pulses has been controlled by appropriate adjustment of a grating-pair compressor. It was found that the skewness of the laser pulse envelope is particularly sensitive to the third-order component of the spectral phase. Introducing such a third-order phase offset by detuning the grating pair relative to the optimum pulse compression settings allowed the generation of skewed pulses. As an example of an application, these skewed pulses were used to optimize a laser-plasma electron accelerator.

Group velocity and pulse lengthening of mismatched laser pulses in plasma channels

Analytic solutions are presented to the non-paraxial wave equation describing an ultra-short, low-power, laser pulse propagating in a plasma channel. Expressions for the laser pulse centroid motion and laser group velocity are derived, valid for matched and mismatched propagation in a parabolic plasma channel, as well as in vacuum, for an arbitrary Laguerre-Gaussian laser mode. The group velocity of a mismatched laser pulse, for which the laser spot size is strongly oscillating, is found to be independent of propagation distance and significantly less than that of a matched pulse. Laser pulse lengthening of a mismatched pulse owing to laser mode slippage is examined and found to dominate over that due to dispersive pulse spreading for sufficiently long pulses. Analytic results are shown to be in excellent agreement with numerical solutions of the full Maxwell equations coupled to the plasma response. Implications for plasma channel diagnostics are discussed.

Femtosecond spectroscopy with vacuum ultraviolet pulse pairs

We combine different wavelengths from an intense high-order harmonics source with variable delay at the focus of a split-mirror interferometer to conduct pump-probe experiments on gas-phase molecules. We report measurements of the time resolution (<44 fs) and spatial profiles (4 μm × 12 μm) at the focus of the apparatus. We demonstrate the utility of this two-color, high-order-harmonic technique by time resolving molecular hydrogen elimination from C(2)H(4) excited into its absorption band at 161 nm.