Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction.

Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

Electronic State Population Dynamics upon Ultrafast Strong Field Ionization and Fragmentation of Molecular Nitrogen.

Air lasing from single ionized N_{2}^{+} molecules induced by laser filamentation in air has been intensively investigated and the mechanisms responsible for lasing are currently highly debated. We use ultrafast nitrogen K-edge spectroscopy to follow the strong field ionization and fragmentation dynamics of N_{2} upon interaction with an ultrashort 800 nm laser pulse. Using probe pulses generated by extreme high-order harmonic generation, we observe transitions indicative of the formation of the electronic ground X^{2}Σ_{g}^{+}, first excited A^{2}Π_{u}, and second excited B^{2}Σ_{u}^{+} states of N_{2}^{+} on femtosecond timescales, from which we can quantitatively determine the time-dependent electronic state population distribution dynamics of N_{2}^{+}. Our results show a remarkably low population of the A^{2}Π_{u} state, and nearly equal populations of the X^{2}Σ_{g}^{+} and B^{2}Σ_{u}^{+} states. In addition, we observe fragmentation of N_{2}^{+} into N and N^{+} on a timescale of several tens of picoseconds that we assign to significant collisional dynamics in the plasma, resulting in dissociative excitation of N_{2}^{+}.

Time-resolving the UV-initiated photodissociation dynamics of OCS.

We present a time-resolved study of the photodissociation dynamics of OCS after UV-photoexcitation at λ = 237 nm. OCS molecules (X1Σ+) were primarily excited to the 11A'' and the 21A' Renner-Teller components of the 1Σ- and 1Δ states. Dissociation into CO and S fragments was observed through time-delayed strong-field ionisation and imaging of the kinetic energy of the resulting CO+ and S+ fragments by intense 790 nm laser pulses. Surprisingly, fast oscillations with a period of ∼100 fs were observed in the S+ channel of the UV dissociation. Based on wavepacket-dynamics simulations coupled with a simple electrostatic-interaction model, these oscillations do not correspond to the known highly-excited rotational motion of the leaving CO(X1Σ+, J ≫ 0) fragments, which has a timescale of ∼140 fs. Instead, we suggest to assign the observed oscillations to the excitation of vibrational wavepackets in the 23A'' or 21A'' states of the molecule that predissociate to form S(3PJ) photoproducts.

Generation of above-terawatt 1.5-cycle visible pulses at 1 kHz by post-compression in a hollow fiber.

We report on the generation of 6.1 mJ, 3.8 fs pulses by the compression of a kilohertz Ti:sapphire laser in a large-aperture long hollow fiber. In order to find optimal conditions for spectral broadening at high pulse energies, we explore different parameter ranges where ionization or the Kerr effect dominates. After identifying the optimum parameter settings, large spectral broadening at high waveguide transmission is obtained. The intense 1.5-cycle pulses are used for high-harmonic generation in argon and neon.

Evolution of a Molecular Shape Resonance along a Stretching Chemical Bond.

We report experiments on laser-assisted electron recollisions that result from strong-field ionization of photoexcited I_{2} molecules in the regime of low-energy electron scattering (<25 eV impact energy). By comparing differential scattering cross sections extracted from the angle-resolved photoelectron spectra to differential scattering cross sections from quantum-scattering calculations, we demonstrate that the electron-scattering dynamics is dominated by a shape resonance. When the molecular bond stretches during the evolution of a vibrational wave packet this shape resonance shifts to lower energies, both in experiment and theory. We explain this behavior by the nature of the resonance wave function, which closely resembles an antibonding molecular orbital of I_{2}.

Atomic-resolution imaging of carbonyl sulfide by laser-induced electron diffraction.

Measurements on the strong-field ionization of carbonyl sulfide molecules by short, intense, 2 µm wavelength laser pulses are presented from experiments where angle-resolved photoelectron distributions were recorded with a high-energy velocity map imaging spectrometer, designed to reach a maximum kinetic energy of 500 eV. The laser-field-free elastic-scattering cross section of carbonyl sulfide was extracted from the measurements and is found in good agreement with previous experiments, performed using conventional electron diffraction. By comparing our measurements to the results of calculations, based on the quantitative rescattering theory, the bond lengths and molecular geometry were extracted from the experimental differential cross sections to a precision better than ±5 pm and in agreement with the known values.

Low-Energy Electron Emission in the Strong-Field Ionization of Rare Gas Clusters.

Clusters and nanoparticles have been widely investigated to determine how plasmonic near fields influence the strong-field induced energetic electron emission from finite systems. We focus on the contrary, i.e., the slow electrons, and discuss a hitherto unidentified low-energy structure (LES) in the photoemission spectra of rare gas clusters in intense near-infrared laser pulses. For Ar and Kr clusters we find, besides field-driven fast electrons, a robust and nearly isotropic emission of electrons with <4 eV kinetic energies that dominates the total yield. Molecular dynamics simulations reveal a correlated few-body decay process involving quasifree electrons and multiply excited ions in the nonequilibrium nanoplasma that results in a dominant LES feature. Our results indicate that the LES emission occurs after significant nanoplasma expansion, and that it is a generic phenomenon in intense laser nanoparticle interactions, which is likely to influence the formation of highly charged ions.

Coulomb explosion imaging of CH3I and CH2ClI photodissociation dynamics.

The photodissociation dynamics of CH3I and CH2ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH2ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

Ion-ion coincidence imaging at high event rate using an in-vacuum pixel detector.

A new ion-ion coincidence imaging spectrometer based on a pixelated complementary metal-oxide-semiconductor detector has been developed for the investigation of molecular ionization and fragmentation processes in strong laser fields. Used as a part of a velocity map imaging spectrometer, the detection system is comprised of a set of microchannel plates and a Timepix detector. A fast time-to-digital converter (TDC) is used to enhance the ion time-of-flight resolution by correlating timestamps registered separately by the Timepix detector and the TDC. In addition, sub-pixel spatial resolution (<6 µm) is achieved by the use of a center-of-mass centroiding algorithm. This performance is achieved while retaining a high event rate (104 per s). The spectrometer was characterized and used in a proof-of-principle experiment on strong field dissociative double ionization of carbon dioxide molecules (CO2), using a 400 kHz repetition rate laser system. The experimental results demonstrate that the spectrometer can detect multiple ions in coincidence, making it a valuable tool for studying the fragmentation dynamics of molecules in strong laser fields.

Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera.

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

Ionization Avalanching in Clusters Ignited by Extreme-Ultraviolet Driven Seed Electrons.

We study the ionization dynamics of Ar clusters exposed to ultrashort near-infrared (NIR) laser pulses for intensities well below the threshold at which tunnel ionization ignites nanoplasma formation. We find that the emission of highly charged ions up to Ar^{8+} can be switched on with unit contrast by generating only a few seed electrons with an ultrashort extreme-ultraviolet (XUV) pulse prior to the NIR field. Molecular dynamics simulations can explain the experimental observations and predict a generic scenario where efficient heating via inverse bremsstrahlung and NIR avalanching is followed by resonant collective nanoplasma heating. The temporally and spatially well-controlled injection of the XUV seed electrons opens new routes for controlling avalanching and heating phenomena in nanostructures and solids, with implications for both fundamental and applied laser-matter science.

Bright attosecond soft X-ray pulse trains by transient phase-matching in two-color high-order harmonic generation.

We study two-color high-order harmonic generation in Neon with 790 nm and 1300 nm driving laser fields and observe an extreme-ultraviolet continuum that extends to photon energies of 160 eV. Using a 6-mm-long, high pressure gas cell, we optimize the HHG yield at high photon energies and investigate the effect of ionization and propagation under phase-matching conditions that allow us to control the temporal structure of the XUV emission. Numerical simulations that include the 3D propagation of the two-color laser pulse show that a bright isolated attosecond pulse with exceptionally high photon energies can be generated in our experimental conditions due to an efficient hybrid optical and phase-matching gating mechanism.

Probing the structure and dynamics of molecular clusters using rotational wave packets.

Rotational wave packets of the weakly bound C(2)H(2)-He complex have been created using impulsive alignment. The coherent rotational dynamics were monitored for 600 ps enabling extraction of a frequency spectrum showing multiple rotational energy levels up to J = 4. spectrum has been combined with ab initio calculations to show that the complex has a highly delocalized structure and is bound only by ca. 7 cm(-1). The experiments demonstrate how highly featured rotational spectra can be obtained from an extremely cold environment where only the lowest rotational energy states are initially populated.

Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane.

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

Photoelectron imaging of XUV photoionization of CO2 by 13-40 eV synchrotron radiation.

Valence band photoionization of CO2 has been studied by photoelectron spectroscopy using a velocity map imaging spectrometer and synchrotron radiation. The measured data allow retrieving electronic and vibrational branching ratios, vibrationally resolved asymmetry parameters, and the total electron yield which includes multiple strong resonances. Additionally, the spectrum of low kinetic energy electrons has been studied in the resonant region, and the evolution with photon energy of one of the forbidden transitions present in the slow photoelectrons spectrum has been carefully analyzed, indicating that in the presence of auto-ionizing resonances the vibrational populations of the ion are significantly redistributed.

Time-Resolved X-ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge.

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.

Picosecond pulse-shaping for strong three-dimensional field-free alignment of generic asymmetric-top molecules.

Fixing molecules in space is a crucial step for the imaging of molecular structure and dynamics. Here, we demonstrate three-dimensional (3D) field-free alignment of the prototypical asymmetric top molecule indole using elliptically polarized, shaped, off-resonant laser pulses. A truncated laser pulse is produced using a combination of extreme linear chirping and controlled phase and amplitude shaping using a spatial-light-modulator (SLM) based pulse shaper of a broadband laser pulse. The angular confinement is detected through velocity-map imaging of H+ and C2+ fragments resulting from strong-field ionization and Coulomb explosion of the aligned molecules by intense femtosecond laser pulses. The achieved three-dimensional alignment is characterized by comparing the result of ion-velocity-map measurements for different alignment directions and for different times during and after the alignment laser pulse to accurate computational results. The achieved strong three-dimensional field-free alignment of [Formula: see text] demonstrates the feasibility of both, strong three-dimensional alignment of generic complex molecules and its quantitative characterization.

Highly efficient soft x-ray spectrometer for transient absorption spectroscopy with broadband table-top high harmonic sources.

We present a novel soft x-ray spectrometer for ultrafast absorption spectroscopy utilizing table-top femtosecond high-order harmonic sources. Where most commercially available spectrometers rely on spherical variable line space gratings with a typical efficiency on the order of 3% in the first diffractive order, this spectrometer, based on a Hettrick-Underwood design, includes a reflective zone plate as a dispersive element. An improved efficiency of 12% at the N K-edge is achieved, accompanied by a resolving power of 890. The high performance of the soft x-ray spectrometer is further demonstrated by comparing nitrogen K-edge absorption spectra from calcium nitrate in aqueous solution obtained with our high-order harmonic source to previous measurements performed at the electron storage ring facility BESSY II.