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We report an experiment to measure the femtosecond electric field of the signal emitted from an optical third-order nonlinear interaction in carbon dioxide molecules. Using degenerate four-wave mixing with femtosecond near infrared laser pulses in combination with the ultra-weak femtosecond pulse measurement technique of TADPOLE, we measure the nonlinear signal electric field in the time domain at different time delays between the interacting pulses. The chirp extracted from the temporal phase of the emitted nonlinear signal is found to sensitively depend on the electronic and rotational contributions to the nonlinear response. While the rotational contribution results in a nonlinear signal chirp close to the chirp of the input pulses, the electronic contribution results in a significantly higher chirp which changes with time delay. Our work demonstrates that electric field-resolved nonlinear spectroscopy offers detailed information on nonlinear interactions at ultrafast time scales., 8 pages, 4 figures, and supplemental document

Two-photon-excited fluorescence spectroscopy is a powerful tool to study the structural and electronic properties of optically active complexes and molecules. Although numerous lanthanide complexes have been characterized by two-photon-excited fluorescence in solution, this report is the first to apply such a technique to actinide compounds. Contrasting with previous observations in lanthanides, we demonstrate that the two-photon absorption properties of the complexes significantly depend on the metal (4f vs 5f), with Cm(III) complexes showing significantly higher two-photon absorption cross sections than lanthanide analogues and up to 200-fold stronger emission intensities. These results are consistent with electronic and structural differences between the lanthanide and actinide systems studied. Hence, the described methodology can provide valuable insights into the interactions between f-elements and ligands, along with promising prospects on the characterization of scarce compounds.

Description, Clusters in 3He and 4He nanodroplets reveal markedly different shapes showcasing the effect of superfluidity on aggregation., Quantum fluid droplets made of helium-3 (3He) or helium-4 (4He) isotopes have long been considered as ideal cryogenic nanolabs, enabling unique ultracold chemistry and spectroscopy applications. The droplets were believed to provide a homogeneous environment in which dopant atoms and molecules could move and react almost as in free space but at temperatures close to absolute zero. Here, we report ultrafast x-ray diffraction experiments on xenon-doped 3He and 4He nanodroplets, demonstrating that the unavoidable rotational excitation of isolated droplets leads to highly anisotropic and inhomogeneous interactions between the host matrix and enclosed dopants. Superfluid 4He droplets are laced with quantum vortices that trap the embedded particles, leading to the formation of filament-shaped clusters. In comparison, dopants in 3He droplets gather in diffuse, ring-shaped structures along the equator. The shapes of droplets carrying filaments or rings are direct evidence that rotational excitation is the root cause for the inhomogeneous dopant distributions.

${\mathrm{D}}_{2}$ molecules, excited by linearly cross-polarized femtosecond extreme ultraviolet (XUV) and near-infrared (NIR) light pulses, reveal highly structured ${\mathrm{D}}^{+}$ ion fragment momenta and angular distributions that originate from two different four-step dissociative ionization pathways after four-photon absorption (one XUV $+$ three NIR). We show that, even for very low dissociation kinetic energy release $\ensuremath{\le}$ 240 meV, specific electronic excitation pathways can be identified and isolated in the final ion momentum distributions. With the aid of ab initio electronic structure and time-dependent Schr\"odinger equation calculations, angular momentum, energy, and parity conservation are used to identify the excited neutral molecular states and molecular orientations relative to the polarization vectors in these different photoexcitation and dissociation sequences of the neutral ${\mathrm{D}}_{2}$ molecule and its ${\mathrm{D}}_{2}^{+}$ cation. In one sequential photodissociation pathway, molecules aligned along either of the two light polarization vectors are excluded, while another pathway selects molecules aligned parallel to the light propagation direction. The evolution of the nuclear wave packet on the intermediate $B{\phantom{\rule{0.16em}{0ex}}}^{1}{\mathrm{\ensuremath{\Sigma}}}_{u}^{+}$ electronic state of the neutral ${\mathrm{D}}_{2}$ molecule is also probed in real time.

Author(s): Verma, D; O'Connell, SMO; Feinberg, AJ; Erukala, S; Tanyag, RMP; Bernando, C; Pang, W; Saladrigas, CA; Toulson, BW; Borgwardt, M; Shivaram, N; Lin, MF; Al Haddad, A; Jager, W; Bostedt, C; Walter, P; Gessner, O; Vilesov, AF | Abstract: Previous single-pulse extreme ultraviolet and x-ray coherent diffraction studies revealed that superfluid He4 droplets obtained in a free jet expansion acquire sizable angular momentum, resulting in significant centrifugal distortion. Similar experiments with normal fluid He3 droplets may help elucidate the origin of the large degree of rotational excitation and highlight similarities and differences of dynamics in normal and superfluid droplets. Here, we present a comparison of the shapes of isolated He3 and He4 droplets following expansion of the corresponding fluids in vacuum at temperatures as low as ∼2 K. Large He3 and He4 droplets with average radii of ∼160 and ∼350 nm, respectively, were produced. We find that the majority of the shapes of He3 droplets in the beam correspond to rotating oblate spheroids, in agreement with previous observations for He4 droplets. The aspect ratio of the droplets is related to the degree of their rotational excitation, which is discussed in terms of reduced angular momenta (Λ) and reduced angular velocities (ω), the average values of which are found to be similar in both isotopes. This similarity suggests that comparable mechanisms induce rotation regardless of the isotope. We hypothesize that the observed distribution of droplet sizes and angular momenta originates from processes in the dense region close to the nozzle, where a significant velocity spread and frequent collisions between droplets induces excessive rotation followed by droplet fission.

We report a novel experimental technique to investigate ultrafast dynamics in photoexcited molecules by probing the third-order nonlinear optical susceptibility. A non-colinear 3-pulse scheme is developed to probe the ultrafast dynamics of excited electronic states using the optical Kerr effect by time-resolved polarization spectroscopy. Optical heterodyne and optical homodyne detection are demonstrated to measure the third-order nonlinear optical response for the S1 excited state of liquid nitrobenzene, which is populated by 2-photon absorption of a 780 nm 35 fs excitation pulse., 12 pages, 4 figures. Changes from previous version: added panel labels to figures 3-4

Free-electron lasers provide a source of x-ray pulses short enough and intense enough to drive nonlinearities in molecular systems. Impulsive interactions driven by these x-ray pulses provide a way to create and probe valence electron motions with high temporal and spatial resolution. Observing these electronic motions is crucial to understand the role of electronic coherence in chemical processes. A simple nonlinear technique for probing electronic motion, impulsive stimulated x-ray Raman scattering (ISXRS), involves a single impulsive interaction to produce a coherent superposition of electronic states. We demonstrate electronic population transfer via ISXRS using broad bandwidth (5.5eV full width at half maximum) attosecond x-ray pulses produced by the Linac Coherent Light Source. The impulsive excitation is resonantly enhanced by the oxygen 1s→2π^{*} resonance of nitric oxide (NO), and excited state neutral molecules are probed with a time-delayed UV laser pulse.

Author(s): Nadgir, A; Thurston, R; Larsen, KA; Shivaram, N; Brister, MM; Slaughter, DS | Abstract: We describe a software implementation of a multi-channel, multi-frequency Lock-in Amplifier (SILIA) to extract modulated signals from noisy data distributed over multiple channels of arbitrary number and size. This software implementation emulates the functionality of a multi-channel, multi-frequency lock-in amplifier in a post-processing step following data acquisition. Unlike most traditional lock-in amplifiers, SILIA can work with any number of input channels and is especially useful to analyze data distributed over many channels. We demonstrate the versatility and performance for extracting weak signals in spectroscopy and fluorescence microscopy. We also discuss more general applications and exhibit a method to automatically estimate error from a lock-in result.

Author(s): Iskandar, W; Gatton, AS; Gaire, B; Sturm, FP; Larsen, KA; Champenois, EG; Shivaram, N; Moradmand, A; Williams, JB; Berry, B; Severt, T; Ben-Itzhak, I; Metz, D; Sann, H; Weller, M; Schoeffler, M; Jahnke, T; Dorner, R; Slaughter, D; Weber, T | Abstract: We have conducted an experimental study on the photo double ionization (PDI) of carbon-dioxide dimers at photon energies of 37 and 55 eV and oxygen dimers at photon energies of 38, 41.5, and 46 eV, while focusing on the dissociation dynamics upon single-photon absorption. The investigation was performed by applying the cold-target recoil-ion momentum spectroscopy method in order to collect and record the three-dimensional momenta of the ionic fragments and emitted electrons from the dissociating dimer in coincidence. The kinetic-energy release upon fragmentation and the electron angular distributions in the laboratory and body-fixed frames, as well as the relative electron-electron emission angle, show unambiguous experimental evidence of intermolecular Coulombic decay (ICD) in carbon-dioxide dimers upon photoionization below and above the double-ionization threshold of CO2 monomers. The PDI of oxygen dimers is less conclusive and shows contributions from ICD and knock-off ionization mechanisms. As for atomic dimers, the present results reveal that ICD in CO2 dimers after valence PDI can also serve as a source for low-energy electrons, known to be very relevant in biological systems, cells, and tissues.

We investigate ultrafast dynamics of the lowest singlet excited electronic state in liquid nitrobenzene using Ultrafast Transient Polarization Spectroscopy (UTPS), extending the well-known technique of Optical-Kerr Effect (OKE) spectroscopy to excited electronic states. The third-order non-linear response of the excited molecular ensemble is highly sensitive to details of excited state character and geometries and is measured using two femtosecond pulses following a third femtosecond pulse that populates the S1 excited state. By measuring this response as a function of time delays between the three pulses involved, we extract the dephasing time of the wave-packet on the excited state. The dephasing time measured as a function of time-delay after pump excitation shows oscillations indicating oscillatory wave-packet dynamics on the excited state. From the experimental measurements and supporting theoretical calculations, we deduce that the wave-packet completely leaves the S1 state surface after three traversals of the inter-system crossing between the singlet S1 and triplet T2 states., Comment: Manuscript 15 pages, 4 figures, 1 table. Supporting Information 5 pages

The quantum mechanical motion of electrons in molecules and solids occurs on the sub-femtosecond timescale. Consequently, the study of ultrafast electronic phenomena requires thegeneration of laser pulses shorter than 1 fs and of sufficient intensity to interact with their targetwith high probability. Probing these dynamics with atomic-site specificity requires the extensionof sub-femtosecond pulses to the soft X-ray spectral region. Here we report the generation of iso-lated soft X-ray attosecond pulses with an X-ray free-electron laser. Our source has a pulse energythat is a million times larger than any other source of isolated attosecond pulses in the soft X-rayspectral region, with a peak power exceeding 100 GW. This unique combination of high intensity,high photon energy and short pulse duration enables the investigation of electron dynamics withX-ray non-linear spectroscopy and single-particle imaging, unlocking a path towards a new era ofattosecond science.

Synopsis We have conducted an experimental study on the photo double ionization (PDI) of carbon dioxide dimers and oxygen dimers, while focusing on the dissociation dynamics upon single photon absorption. The results in terms of the kinetic energy and angular distributions of the charged particles show unambiguous experimental evidence of intermolecular Coulombic decay (ICD) in carbon dioxide dimers. In the oxygen dimer, the results show that ICD is accompanied by knock-off ionization mechanisms.

Author(s): Ranitovic, P; Sturm, FP; Tong, XM; Wright, TW; Ray, D; Zalyubovskya, I; Shivaram, N; Belkacem, A; Slaughter, DS; Weber, T | Abstract: 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 O2+∗ 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.

The electronic and nuclear dynamics in methanol, following 156~nm photoexcitation, are investigated by combining a detailed analysis of time-resolved photoelectron spectroscopy experiments with electronic structure calculations. The photoexcitation pump pulse is followed by a delayed 260~nm photoionization probe pulse, to produce photoelectrons that are analyzed by velocity map imaging. The yield of mass-resolved ions, measured with similar experimental conditions, are found to exhibit the same time-dependence as specific photoelectron spectral features. Energy-resolved signal onset and decay times are extracted from the measured photoelectron spectra to achieve high temporal resolution, beyond the 20~fs pump and probe pulse durations. When combined with {\it ab initio} calculations of selected cuts through the excited state potential energy surfaces, this information allows the dynamics of the transient excited molecule, which exhibits multiple nuclear and electronic degrees of freedom, to be tracked on its intrinsic few-femtosecond timescale. Within 15~fs of photoexcitation, we observe nuclear motion on the initially bound photoexcited 2$^{1}$A$''$ (S$_2$) electronic state, through a conical intersection with the 1$^{1}$A$'$ (S$_3$) state, which reveals paths to photodissociation following C--O stretch and C--O--H angle opening., 8 pages, 5 figures + Supporting Info

We present a study of the ultrafast dissociation dynamics of the lowest-lying electronic excited states in ${\mathrm{CO}}_{2}$ 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 $^{1}{\mathrm{\ensuremath{\Pi}}}_{g}$ 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 $\ensuremath{\sim}133$ fs.

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 H2 molecules. A nuclear wave packet is created in the BΣu+1 state of the neutral H2 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 BΣu+1 electronic state, the effective H2+ 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 H2∗, the interpretation of the nonequilibrium multiphoton and multicolor ionization processes is still a challenging task, requiring intricate theoretical analysis, We acknowledge many fruitful discussions and advice from R. Dorner, M. S. Schoffler, L. Ph. Schmidt, and Wei Cao. We are indebted to O. Jagutzki and A. Czasch from Roentdek GmbH and T. Jahnke from Cronologic GmbH for outstanding support for their momentum imaging detectors readout and software. F.S. acknowledges financial support by Studienstiftung des deutschen Volkes. A.P. and F.M.acknowledge the European COST Action XLIC CM1204, the European Research Council Advanced Grant XCHEM No. 290853, and the MINECO Project No. FIS2013-42002-R. X.M.T. was supported by a Grand-in-Aid for Scientific Research from the Japan Society for the Promotion of Science and Interdisciplinary Computational Science Program in Center for Computational Sciences, University of Tsukuba. This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, and by the Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at LBNL under Contract No. DE-AC02-05CH11231

We present experimental results and a theoretical framework for understanding the ionization dynamics in atoms exposed to XUV attosecond pulse trains and strong multi-cycle infrared (IR) fields. We invoke the Floquet formalism to model dressed atomic states as a manifold of Fourier components spaced by the laser frequency. In XUV-IR pump–probe measurements, we observe that the ionization yield oscillates due to quantum interference between photo-excitation paths to a Floquet state. We show that the intensity-dependent shifts of atomic structure modify the ionization channels and the associated interference phase. We extract this phase variation and compare it with simulations. These results provide a comprehensive description of the two-color ionization process and enable new schemes for control of attosecond ionization and fragmentation dynamics.

© 2016 Author(s). 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.

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 (

Spatial light modulators (SLMs) are a versatile tool for teaching optics, but the cost associated with an SLM setup prevents its adoption in many undergraduate and graduate optics labs. We describe a simple method for creating a low-cost SLM by extracting components from a commercial LCD projector. We demonstrate the pedagogical applications of this SLM design by providing examples of its use in teaching diffraction and interference phenomena. We also discuss an SLM’s potential as a research tool in graduate labs. In particular, we demonstrate its use in holography and in the generation of optical vortices.

The coherent evolution of an electron hole in a photoionized molecule represents an unexplored facet of charge transfer phenomena occurring in complex systems. Using ultrafast extreme ultraviolet spectroscopy, we investigate the real-time dynamics of an electron hole wave packet created near a conical intersection in ${\mathrm{CO}}_{2}$. We resolve the oscillation of the electron hole density between $\ensuremath{\sigma}$ and $\ensuremath{\pi}$ character, driven by the coupled bending and asymmetric stretch vibrations of the molecule. We also quantify the mixing between electron hole configurations and find that the wave packet coherence diminishes with time due to thermal dephasing.

We investigate electron wavepacket dynamics in Helium using an attosecond pulse train to prepare a superposition of states. The wavepacket is probed by a femtosecond infrared pulse on a 900 femtosecond timescale with attosecond resolution.

© 2016 Optical Society of America. 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.

Using ultrafast extreme ultraviolet pulses, we performed a direct measurement of the relaxation dynamics of neutral superexcited states corresponding to the nl\sigma_g(c^4\Sigma_u^-) Rydberg series of O_2. An XUV attosecond pulse train was used to create a temporally localized Rydberg wavepacket and the ensuing electronic and nuclear dynamics were probed using a time-delayed femtosecond near-infrared pulse. We investigated the competing predissociation and autoionization mechanisms for superexcited molecules and found that autoionization is dominant for the low n Rydberg states. We measured an autoionization lifetime of 92+/-6 fs and 180+/-10 fs for (5s,4d)\sigma_g and (6s,5d)\sigma_g Rydberg state groups respectively. We determine that the disputed neutral dissociation lifetime for the \nu=0 vibrational level of the Rydberg series is 1100+/-100fs., Comment: 5 pages, 4 figures

Using high-order harmonic attosecond pulse trains, we investigate the photoionization dynamics and transient electronic structure of a helium atom in the presence of moderately strong ($\ensuremath{\sim}{10}^{12}\text{ }\text{ }\mathrm{W}\text{ }{\mathrm{cm}}^{\ensuremath{-}2}$) femtosecond laser pulses. We observe quantum interferences between photoexcitation paths from the ground state to different laser-dressed Floquet state components. As the intensity ramps on femtosecond time scales, we observe switching between ionization channels mediated by different atomic resonances. Using precision measurements of ion yields and photoelectron distributions, the quantum phase difference between interfering paths is extracted for each ionization channel and compared with simulations. Our results elucidate photoionization mechanisms in strong fields and open the doors for photoabsorption or photoionization control schemes.

We demonstrate the key role played by the spatial characteristics and focusing conditions of a femtosecond multi-cycle laser pulse in optimization of filament output for the purpose of obtaining compressed light pulses in the few-cycle regime. We find that for a given beam profile and focal parameters, driving the filament with energy above a certain limiting value can negatively impact pulse compression. However, for a given energy, a smaller and cleaner input beam mode obtained by using a hard aperture can substantially improve the pulse compression ability. In addition, we show that a larger focal volume can assist in creation of a shorter output pulse.

Attosecond pump-probe experiments routinely utilize extreme ultraviolet (XUV) and IR fields, with relative phase being the variable parameter. However, the Gouy phase slip between the focused IR and XUV pulses inevitably leads to a certain amount of phase averaging and loss of accuracy. By using ion imaging, we establish a one-to-one mapping between the local phase slip and the spatial coordinates of the focal volume, thus performing in situ characterization of the Gouy phase of a complex beam and its role in ionization of He and Xe. We demonstrate that spatially discriminated ion imaging enhances the contrast of a phase-dependent XUV+IR ionization signal. We utilize our technique to unmask a weak ionization asymmetry, thus opening pathways for further high-precision attosecond studies.

We utilize ion-imaging to perform a detailed characterization of the effects of Gouy phase mismatch and wave-front distortions on attosecond resolved, pump-probe measurements of XUV/IR and IR/IR ionization of He and Xe atoms.

The evolution of electron wavepackets determines the course of many physical and chemical phenomena and attosecond spectroscopy aims to measure and control such dynamics in real-time. Here, we investigate radial electron wavepacket motion in Helium by using an XUV attosecond pulse train to prepare a coherent superposition of excited states and a delayed femtosecond IR pulse to ionize them. Quantum beat signals observed in the high resolution photoelectron spectrogram allow us to follow the field-free evolution of the bound electron wavepacket and determine the time-dependent ionization dynamics of the low-lying 2p state., Comment: 10 pages, 6 figures

We investigate the coherent motion of an electron hole wavepacket near a conical intersection in CO2. These results demonstrate the sensitivity of attosecond, XUV sources in probing and controlling charge transfer dynamics occurring in nature.