Controlling laser-dressed resonance line shape using attosecond extreme-ultraviolet pulse with a spectral minimum.

High-harmonic generation from a gas target exhibits sharp spectral features and rapid phase variation near the Cooper minimum. By applying spectral filtering, shaped isolated attosecond pulses can be generated where the pulse is split into two in the time domain. Using such shaped extreme-ultraviolet (XUV) pulses, we theoretically study attosecond transient absorption (ATA) spectra of helium [Formula: see text] autoionizing state which is resonantly coupled to the [Formula: see text] dark state by a time-delayed infrared laser. Our simulations show that the asymmetric [Formula: see text] Fano line shape can be readily tuned into symmetric Lorentzian within the time delay of a few tens of attoseconds. Such efficient control is due to the destructive interference in the generation of the [Formula: see text] state when it is excited by a strongly shaped XUV pulse. This is to be compared to prior experiments where tuning the line shape of a Fano resonance would take tens of femtoseconds. We also show that the predicted ATA spectral line shape can be observed experimentally after propagation in a gas medium. Our results suggest that strongly shaped attosecond XUV pulses offer the opportunity for controlling and probing fine features of narrow resonances on the few-ten attoseconds timescale.

Role of the Porras factor in phase matching of high-order harmonic generation driven by focused few-cycle laser pulses.

We investigate the role of the Porras factor (or laser focusing effect) on the macroscopic high-order harmonic generation (HHG) driven by a focused broadband few-cycle laser beam. By employing a non-adiabatic phase-matching analysis method, we reveal that phase mismatch due to the induced-dipole phase varies with the Porras factor, which is dominant in phase matching at low gas pressure. We also find that in a strongly ionized medium when gas pressure is high, the nonlinear propagation is dominated by a plasma effect such that the focusing effect is mitigated, resulting in similar poor phase matching of HHG regardless of the Porras factor. Our results are expected to assist experimentalists identifying optimal conditions for HHG using ultrashort laser pulses.

Imaging the Renner-Teller effect using laser-induced electron diffraction.

Structural information on electronically excited neutral molecules can be indirectly retrieved, largely through pump-probe and rotational spectroscopy measurements with the aid of calculations. Here, we demonstrate the direct structural retrieval of neutral carbonyl disulfide (CS2) in the [Formula: see text] excited electronic state using laser-induced electron diffraction (LIED). We unambiguously identify the ultrafast symmetric stretching and bending of the field-dressed neutral CS2 molecule with combined picometer and attosecond resolution using intrapulse pump-probe excitation and measurement. We invoke the Renner-Teller effect to populate the [Formula: see text] excited state in neutral CS2, leading to bending and stretching of the molecule. Our results demonstrate the sensitivity of LIED in retrieving the geometric structure of CS2, which is known to appear as a two-center scatterer.

Reported Signs, Symptoms, and Diagnostic Tests Before Cardiotoxicity Among Women With Breast Cancer: A Pilot Study.

BACKGROUND: Cardiotoxicity after cancer treatment is a potentially preventable life-threatening complication among women with breast cancer. There is no algorithm to identify women with breast cancer at risk of cardiotoxicity. OBJECTIVES: We quantified signs and symptoms as well as selected laboratory values among women with breast cancer who developed cardiotoxicity. METHODS: The clinical characteristics (n = 15) were collected from electronic health records. Spearman correlation coefficients and a nonparametric statistical test were used to analyze data. RESULTS: Significant statistical differences were detected in the laboratory values comparing the first and second half of 6 months before cardiotoxicity including alanine aminotransferase (U/L) (30.67 ± 26.27 and 42.31 ± 35.65, respectively; P = .03, Cohen's d = 0.37). A negative correlation was found between estimated glomerular filtration rate and new onset of more than 1 sign or symptom (Spearman's ρ = -0.5, P = .06). CONCLUSIONS: Investigating clinical characteristics before cardiotoxicity may determine the mechanism(s) and identify high-risk patients.

Optimal generation and isolation of attosecond pulses in an overdriven ionized medium.

We identify optimal conditions for the generation and isolation of attosecond pulses in an overdriven ionized medium. In a high-pressure and highly ionized gas, the spatiotemporal wavefront rotation of a driving laser can be optimized, leading to complete spatial separation of successive attosecond bursts in the far field. The resulting isolated attosecond pulses (IAPs) are much more divergent such that they are spatially separated from the driving laser in the far field. We show that the time delay of near-field harmonic emission along the radial distance determines the divergence of the attosecond burst in the far field. The generated IAPs are phase matched upon propagation in the second half of the gas medium. Validity of the generation scheme is tested at different carrier-envelope phases for a few-cycle laser pulse and by synthesizing the fundamental and its second harmonic field for a long-duration pulse.

Two-dimensional retrieval methods for ultrafast imaging of molecular structure using laser-induced electron diffraction.

Molecular structural retrieval based on electron diffraction has been proposed to determine the atomic positions of molecules with sub-angstrom spatial and femtosecond temporal resolutions. Given its success on small molecular systems, in this work, we point out that the accuracy of structure retrieval is constrained by the availability of a wide range of experimental data in the momentum space in all molecular systems. To mitigate the limitations, for laser-induced electron diffraction, here we retrieve molecular structures using two-dimensional (energy and angle) electron momentum spectra in the laboratory frame for a number of small molecular systems, which have previously been studied with 1D methods. Compared to the conventional single-energy or single-angle analysis, our 2D methods effectively expand the momentum range of the measured data. Besides utilization of the 2D data, two complementary methods are developed for consistency check on the retrieved results. The 2D nature of our methods also offers a way of estimating the error from retrieval, which has never been explored before. Comparing with results from prior experiments, our findings show evidence that our 2D methods outperform the conventional 1D methods. Paving the way to the retrieval of large molecular systems, in which their tunneling ionization rates are challenging to obtain, we estimate the error of using the isotropic model in place of including the orientation-dependent ionization rate.

Imaging an isolated water molecule using a single electron wave packet.

Observing changes in molecular structure requires atomic-scale Ångstrom and femtosecond spatio-temporal resolution. We use the Fourier transform (FT) variant of laser-induced electron diffraction (LIED), FT-LIED, to directly retrieve the molecular structure of H2O+ with picometer and femtosecond resolution without a priori knowledge of the molecular structure nor the use of retrieval algorithms or ab initio calculations. We identify a symmetrically stretched H2O+ field-dressed structure that is most likely in the ground electronic state. We subsequently study the nuclear response of an isolated water molecule to an external laser field at four different field strengths. We show that upon increasing the laser field strength from 2.5 to 3.8 V/Å, the O-H bond is further stretched and the molecule slightly bends. The observed ultrafast structural changes lead to an increase in the dipole moment of water and, in turn, a stronger dipole interaction between the nuclear framework of the molecule and the intense laser field. Our results provide important insights into the coupling of the nuclear framework to a laser field as the molecular geometry of H2O+ is altered in the presence of an external field.

Enhanced high-harmonic generation up to the soft X-ray region driven by mid-infrared pulses mixed with their third harmonic.

We systematically study the efficiency enhancement of high-harmonic generation (HHG) in an Ar gas cell up to the soft X-ray (SXR) range using a two-color laser field composed of 2.1 µm (ω) and 700 nm (3ω) with parallel linear polarization. Our experiment follows the recent theoretical investigations that determined two-color mid-infrared (IR) pulses, mixed with their third harmonic (ω + 3ω), to be close to optimal driving waveforms for enhancing HHG efficiency in the SXR region [Jin et al., Nature Comm. 5, 4003 (2014)]. We observed sub-optical-cycle-dependent efficiency enhancements of up to 8.2 of photon flux integrated between 20 - 70 eV, and up to 2.2 between 85 - 205 eV. Enhancement of HHG efficiency was most pronounced for the lowest tested backing pressure (≈ 140 mbar), and decreased monotonically as the pressure was increased. The single-color (ω)-driven HHG was optimal at the highest backing pressure tested in the experiment (≈ 375 mbar). Our numerical simulations based on single-atom response and 3D pulse propagation show good qualitative agreement with experimental observations. The lower enhancement at high pressure and higher photon energy indicates that phase matching of two-color-driven HHG is more sensitive to ionization rate and pulse propagation effects than the single-color case. We show that with further improvements to the relative phase jitter and the spatio-temporal overlap of the two beams, the efficiency enhancement could be further improved by at least a factor of ≈ 2.

Extension of water-window harmonic cutoff by laser defocusing-assisted phase matching.

We extend a recently demonstrated scheme [Optica4, 976 (2017)OPTIC82334-253610.1364/OPTICA.4.000976] to overcome the limit of conventional harmonic cutoff for different pulse durations, laser wavelengths, and gas targets. By tuning the truncation of long wavelength lasers, we show that the defocusing-assisted phase matching (DAPM) can be achieved in a tightly focused beam and highly ionized short gas cell, and can be used to effectively extend the harmonic cutoff energy and optimize its yield. An analysis of phase matching reveals that at longer wavelengths, greater cutoff extension to the water window region is achieved because of the larger harmonic intrinsic phase (proportional to the cube of laser wavelength), and because DAPM works at relatively higher laser intensities using a Ne target. This scheme provides a promising method for efficiently generating intense attosecond light sources in the extreme ultraviolet to x-rays.

Role of the Transition Dipole Amplitude and Phase on the Generation of Odd and Even High-Order Harmonics in Crystals.

Since the first observation of odd and even high-order harmonics generated from ZnO crystals in 2011, the dependence of the harmonic yields on the orientation of the laser polarization with respect to the crystal axis has never been properly interpreted. This failure has been traced to the lack of a correct account of the phase of the transition dipole moment between the valence band and the conduction band. Using a simple one-dimensional two-band model, here we demonstrate that the observed odd harmonics is directly related to the orientation dependence of the magnitude of the transition dipole, while even harmonics is directly related to the phase of the transition dipole. Our result points out the essential role of the complex transition dipole moment in understanding harmonic generation from solids that has long been overlooked so far.

Real-Time Observation of Molecular Spinning with Angular High-Harmonic Spectroscopy.

We demonstrate an angular high-harmonic spectroscopy method to probe the spinning dynamics of a molecular rotation wave packet in real time. With the excitation of two time-delayed, polarization-skewed pump pulses, the molecular ensemble is impulsively kicked to rotate unidirectionally, which is subsequently irradiated by another delayed probe pulse for high-order harmonic generation (HHG). The spatiotemporal evolution of the molecular rotation wave packet is visualized from the time-dependent angular distributions of the HHG yields and frequency shift measured at various polarization directions and time delays of the probe pulse. The observed frequency shift in HHG is demonstrated to arise from the nonadiabatic effect induced by molecular spinning. Different from the previous spectroscopic and Coulomb explosion imaging techniques, the angular high-harmonic spectroscopy method can reveal additionally the electronic structure and multiple orbitals of the sampled molecule. All the experimental findings are well reproduced by numerical simulations. Further extension of this method would provide a powerful tool for probing complex polyatomic molecules with HHG spectroscopy.

Imaging ultrafast molecular dynamics with laser-induced electron diffraction.

Establishing the structure of molecules and solids has always had an essential role in physics, chemistry and biology. The methods of choice are X-ray and electron diffraction, which are routinely used to determine atomic positions with sub-ångström spatial resolution. Although both methods are currently limited to probing dynamics on timescales longer than a picosecond, the recent development of femtosecond sources of X-ray pulses and electron beams suggests that they might soon be capable of taking ultrafast snapshots of biological molecules and condensed-phase systems undergoing structural changes. The past decade has also witnessed the emergence of an alternative imaging approach based on laser-ionized bursts of coherent electron wave packets that self-interrogate the parent molecular structure. Here we show that this phenomenon can indeed be exploited for laser-induced electron diffraction (LIED), to image molecular structures with sub-ångström precision and exposure times of a few femtoseconds. We apply the method to oxygen and nitrogen molecules, which on strong-field ionization at three mid-infrared wavelengths (1.7, 2.0 and 2.3 µm) emit photoelectrons with a momentum distribution from which we extract diffraction patterns. The long wavelength is essential for achieving atomic-scale spatial resolution, and the wavelength variation is equivalent to taking snapshots at different times. We show that the method has the sensitivity to measure a 0.1 Å displacement in the oxygen bond length occurring in a time interval of ∼5 fs, which establishes LIED as a promising approach for the imaging of gas-phase molecules with unprecedented spatio-temporal resolution.

Optimal generation of high harmonics in the water-window region by synthesizing 800-nm and mid-infrared laser pulses.

We propose a method to optimally synthesize a strong 800-nm Ti:sapphire laser pulse and a relatively weak mid-infrared laser pulse to enhance harmonic yields in the water-window region. The required wavelength of the mid-infrared laser is varied from about 2.0 to 3.2 µm. The optimized waveforms generate comparable harmonic yields as the waveforms proposed in [Sci. Rep.4, 7067 (2014)], but with much weaker intensity for the mid-infrared laser. This method provides an alternative scheme based on the available laser technology to help realize tabletop light source in the water-window region by high-order harmonic generation.

Generation of Bright, Spatially Coherent Soft X-Ray High Harmonics in a Hollow Waveguide Using Two-Color Synthesized Laser Pulses.

We investigate the efficient generation of low-divergence high-order harmonics driven by waveform-optimized laser pulses in a gas-filled hollow waveguide. The drive waveform is obtained by synthesizing two-color laser pulses, optimized such that highest harmonic yields are emitted from each atom. Optimization of the gas pressure and waveguide configuration has enabled us to produce bright and spatially coherent harmonics extending from the extreme ultraviolet to soft x rays. Our study on the interplay among waveguide mode, atomic dispersion, and plasma effect uncovers how dynamic phase matching is accomplished and how an optimized waveform is maintained when optimal waveguide parameters (radius and length) and gas pressure are identified. Our analysis should help laboratory development in the generation of high-flux bright coherent soft x rays as tabletop light sources for applications.

Universality of returning electron wave packet in high-order harmonic generation with midinfrared laser pulses.

We show that a returning electron wave packet in high-order harmonic generation (HHG) with midinfrared laser pulses converges to a universal limit for a laser wavelength above about 3 µm. The results are consistent among the different methods: a numerical solution of the time-dependent Schrödinger equation, the strong-field approximation, and the quantum orbits theory. We further analyze how the contribution from different electron "trajectories" survives the macroscopic propagation in the medium. Our result thus provides a new framework for investigating the wavelength scaling law for the HHG yields.

High harmonic spectroscopy of the Cooper minimum in molecules.

The Cooper minimum (CM) has been studied using high harmonic generation solely in atoms. Here, we present detailed experimental and theoretical studies on the CM in molecules probed by high harmonic generation using a range of near-infrared light pulses from λ=1.3 to 1.8 µm. We demonstrate the CM to occur in CS(2) and CCl(4) at ~42 and ~40 eV, respectively, by comparing the high harmonic spectra with the known partial photoionization cross sections of different molecular orbitals, confirmed by theoretical calculations of harmonic spectra. We use CM to probe electron localization in Cl-containing molecules (CCl(4), CH(2)Cl(2), and trans-C(2)H(2)Cl(2)) and show that the position of the minimum is influenced by the molecular environment.

Theory of high harmonic generation for probing time-resolved large-amplitude molecular vibrations with ultrashort intense lasers.

We present a theory that incorporates the vibrational degrees of freedom in a high-order harmonic generation (HHG) process with ultrashort intense laser pulses. In this model, laser-induced time-dependent transition dipoles for each fixed molecular geometry are added coherently, weighted by the laser-driven time-dependent nuclear wave packet distribution. We show that the nuclear distribution can be strongly modified by the HHG driving laser. The validity of this model is first checked against results from the numerical solution of the time-dependent Schrödinger equation for a simple model system. We show that in combination with the established quantitative rescattering theory this model is able to reproduce the time-resolved pump-probe HHG spectra of N(2)O(4) reported by Li et al. [Science 322, 1207 (2008)].

Laser-induced electron diffraction for probing rare gas atoms.

Recently, using midinfrared laser-induced electron diffraction (LIED), snapshots of a vibrating diatomic molecule on a femtosecond time scale have been captured [C.I. Blaga et al., Nature (London) 483, 194 (2012)]. In this Letter, a comprehensive treatment for the atomic LIED response is reported, a critical step in generalizing this imaging method. Electron-ion differential cross sections (DCSs) of rare gas atoms are extracted from measured angular-resolved, high-energy electron momentum distributions generated by intense midinfrared lasers. Following strong-field ionization, the high-energy electrons result from elastic rescattering of a field-driven wave packet with the parent ion. For recollision energies ≥100 eV, the measured DCSs are indistinguishable for the neutral atoms and ions, illustrating the close collision nature of this interaction. The extracted DCSs are found to be independent of laser parameters, in agreement with theory. This study establishes the key ingredients for applying LIED to femtosecond molecular imaging.

Imaging ultrafast dynamics of molecules with laser-induced electron diffraction.

We introduce a laser-induced electron diffraction method (LIED) for imaging ultrafast dynamics of small molecules with femtosecond mid-infrared lasers. When molecules are placed in an intense laser field, both low- and high-energy photoelectrons are generated. According to quantitative rescattering (QRS) theory, high-energy electrons are produced by a rescattering process where electrons born at the early phase of the laser pulse are driven back to rescatter with the parent ion. From the high-energy electron momentum spectra, field-free elastic electron-ion scattering differential cross sections (DCS), or diffraction images, can be extracted. With mid-infrared lasers as the driving pulses, it is further shown that the DCS can be used to extract atomic positions in a molecule with sub-angstrom spatial resolution, in close analogy to the standard electron diffraction method. Since infrared lasers with pulse duration of a few to several tens of femtoseconds are already available, LIED can be used for imaging dynamics of molecules with sub-angstrom spatial and a few-femtosecond temporal resolution. The first experiment with LIED has shown that the bond length of oxygen molecules shortens by 0.1 Å in five femtoseconds after single ionization. The principle behind LIED and its future outlook as a tool for dynamic imaging of molecules are presented.

Filming movies of attosecond charge migration in single molecules with high harmonic spectroscopy.

Electron migration in molecules is the progenitor of chemical reactions and biological functions after light-matter interaction. Following this ultrafast dynamics, however, has been an enduring endeavor. Here we demonstrate that, by using machine learning algorithm to analyze high-order harmonics generated by two-color laser pulses, we are able to retrieve the complex amplitudes and phases of harmonics of single fixed-in-space molecules. These complex dipoles enable us to construct movies of laser-driven electron migration after tunnel ionization of N2 and CO2 molecules at time steps of 50 attoseconds. Moreover, the angular dependence of the migration dynamics is fully resolved. By examining the movies, we observe that electron holes do not just migrate along the laser polarization direction, but may swirl around the atom centers. Our result establishes a general scheme for studying ultrafast electron dynamics in molecules, paving a way for further advance in tracing and controlling photochemical reactions by femtosecond lasers.