Abstract: Since 2012 August Voyager 1 has been observing the local interstellar energy spectra of Galactic cosmic-ray nuclei down to 3 MeV nuc^(−1) and electrons down to 2.7 MeV. The H and He spectra have the same energy dependence between 3 and 346 MeV nuc^(−1), with a broad maximum in the 10–50 MeV nuc^(−1) range and a H/He ratio of 12.2 ± 0.9. The peak H intensity is ~15 times that observed at 1 AU, and the observed local interstellar gradient of 3–346 MeV H is −0.009 ± 0.055% AU^(−1), consistent with models having no local interstellar gradient. The energy spectrum of electrons (e^− + e^+) with 2.7–74 MeV is consistent with E^(−1.30±0.05) and exceeds the H intensity at energies below ~50 MeV. Propagation model fits to the observed spectra indicate that the energy density of cosmic-ray nuclei with >3 MeV nuc^(−1) and electrons with >3 MeV is 0.83–1.02 eV cm−3 and the ionization rate of atomic H is in the range of 1.51–1.64 × 10^(−17) s^(−1). This rate is a factor >10 lower than the ionization rate in diffuse interstellar clouds, suggesting significant spatial inhomogeneity in low-energy cosmic rays or the presence of a suprathermal tail on the energy spectrum at much lower energies. The propagation model fits also provide improved estimates of the elemental abundances in the source of Galactic cosmic rays.

Abstract: The time it takes a bound electron to respond to the electromagnetic force of light sets a fundamental speed limit on the dynamic control of matter and electromagnetic signal processing. Time-integrated measurements of the nonlinear refractive index of matter indicate that the nonlinear response of bound electrons to optical fields is not instantaneous; however, a complete spectral characterization of the nonlinear susceptibility tensors--which is essential to deduce the temporal response of a medium to arbitrary driving forces using spectral measurements--has not yet been achieved. With the establishment of attosecond chronoscopy, the impulsive response of positive-energy electrons to electromagnetic fields has been explored through ionization of atoms and solids by an extreme-ultraviolet attosecond pulse or by strong near-infrared fields. However, none of the attosecond studies carried out so far have provided direct access to the nonlinear response of bound electrons. Here we demonstrate that intense optical attosecond pulses synthesized in the visible and nearby spectral ranges allow sub-femtosecond control and metrology of bound-electron dynamics. Vacuum ultraviolet spectra emanating from krypton atoms, exposed to intense waveform-controlled optical attosecond pulses, reveal a finite nonlinear response time of bound electrons of up to 115 attoseconds, which is sensitive to and controllable by the super-octave optical field. Our study could enable new spectroscopies of bound electrons in atomic, molecular or lattice potentials of solids, as well as light-based electronics operating on sub-femtosecond timescales and at petahertz rates.

Abstract: Visualizing chemical reactions as they occur requires atomic spatial and femtosecond temporal resolution. Here, we report imaging of the molecular structure of acetylene (C 2 H 2 ) 9 femtoseconds after ionization. Using mid-infrared laser–induced electron diffraction (LIED), we obtained snapshots as a proton departs the [C 2 H 2 ] 2+ ion. By introducing an additional laser field, we also demonstrate control over the ultrafast dissociation process and resolve different bond dynamics for molecules oriented parallel versus perpendicular to the LIED field. These measurements are in excellent agreement with a quantum chemical description of field-dressed molecular dynamics.

Abstract: We introduce a series of 20 cosmological hydrodynamical simulations of L⇤ (M200 = 1011.7 − 1012.3M") and group-sized (M200 = 1012.7 − 1013.3M") haloes run with the model used for the EAGLE project, which additionally includes a nonequilibrium ionization and cooling module that follows 136 ions. The simulations reproduce the observed correlation, revealed by COS-Halos at z ⇠ 0.2, between Ovi column density at impact parameters b 106 K) promotes oxygen to higher ionization states, suppressing the Ovi column density. The observed NOvi-sSFR correlation therefore does not imply a causal link, but reflects the changing characteristic ionization state of oxygen as halo mass is increased. In spite of the mass-dependence of the oxygen ionization state, the most abundant circumgalactic oxygen ion in both L⇤ and group haloes is Ovii; Ovi accounts for only 0.1% of the oxygen in group haloes and 0.9-1.3% with L⇤ haloes. Nonetheless, the metals traced by Ovi absorbers represent a fossil record of the feedback history of galaxies over a Hubble time; their characteristic epoch of ejection corresponds to z > 1 and much of the ejected metal mass resides beyond the virial radius of galaxies. For both L⇤ and group galaxies, more of the oxygen produced and released by stars resides in the circumgalactic medium (within twice the virial radius) than in the stars and ISM of the galaxy.

Abstract: Any injection of electromagnetically interacting particles during the cosmic dark ages will lead to increased ionization, heating, production of Lyman-$\ensuremath{\alpha}$ photons and distortions to the energy spectrum of the cosmic microwave background, with potentially observable consequences. In this paper we describe numerical results for the low-energy electrons and photons produced by the cooling of particles injected at energies from keV to multi-TeV scales, at arbitrary injection redshifts (but focusing on the post-recombination epoch). We use these data, combined with existing calculations modeling the cooling of these low-energy particles, to estimate the resulting contributions to ionization, excitation and heating of the gas, and production of low-energy photons below the threshold for excitation and ionization. We compute corrected deposition-efficiency curves for annihilating dark matter, and demonstrate how to compute equivalent curves for arbitrary energy-injection histories. These calculations provide the necessary inputs for the limits on dark matter annihilation presented in the accompanying paper I, but also have potential applications in the context of dark matter decay or deexcitation, decay of other metastable species, or similar energy injections from new physics. We make our full results publicly available at http://nebel.rc.fas.harvard.edu/epsilon, to facilitate further independent studies. In particular, we provide the full low-energy electron and photon spectra, to allow matching onto more detailed codes that describe the cooling of such particles at low energies.

Abstract: Attosecond science has paved the way for direct probing of electron dynamics in gases and solids. This review provides an overview of recent attosecond measurements, focusing on the wealth of knowledge obtained by the application of isolated attosecond pulses in studying dynamics in gases and solid-state systems. Attosecond photoelectron and photoion measurements in atoms reveal strong-field tunneling ionization and a delay in the photoemission from different electronic states. These measurements applied to molecules have shed light on ultrafast intramolecular charge migration. Similar approaches are used to understand photoemission processes from core and delocalized electronic states in metal surfaces. Attosecond transient absorption spectroscopy is used to follow the real-time motion of valence electrons and to measure the lifetimes of autoionizing channels in atoms. In solids, it provides the first measurements of bulk electron dynamics, revealing important phenomena such as the timescales governing the switching from an insulator to a metallic state and carrier-carrier interactions.

Abstract: We investigate microdischarge formation inside catalyst pores by a two-dimensional fluid model for various pore sizes in the μm-range and for various applied voltages. Indeed, this is a poorly understood phenomenon in plasma catalysis. The calculations are performed for a dielectric barrier discharge in helium, at atmospheric pressure. The electron and ion densities, electron temperature, electric field and potential, as well as the electron impact ionization and excitation rate and the densities of excited plasma species, are examined for a better understanding of the characteristics of the plasma inside a pore. The results indicate that the pore size and the applied voltage are critical parameters for the formation of a microdischarge inside a pore. At an applied voltage of 20 kV, our calculations reveal that the ionization mainly takes place inside the pore, and the electron density shows a significant increase near and in the pore for pore sizes larger than 200 μm, whereas the effect of the pore on the total ion density is evident even for 10 μm pores. When the pore size is fixed at 30 μm, the presence of the pore has no significant influence on the plasma properties at an applied voltage of 2 kV. Upon increasing the voltage, the ionization process is enhanced due to the strong electric field and high electron temperature, and the ion density shows a remarkable increase near and in the pore for voltages above 10 kV. These results indicate that the plasma species can be formed inside pores of structured catalysts (in the μm range), and they may interact with the catalyst surface, and affect the plasma catalytic process.

Abstract: Here we present an overview of recent developments of X-ray and electron spectroscopy to probe water at different temperatures. Photon-induced ionization followed by detection of electrons from either the O 1s level or the valence band is the basis of photoelectron spectroscopy. Excitation between the O 1s and the unoccupied states or occupied states is utilized in X-ray absorption and X-ray emission spectroscopies. These techniques probe the electronic structure of the liquid phase and show sensitivity to the local hydrogen-bonding structure. Both experimental aspects related to the measurements and theoretical simulations to assist in the interpretation are discussed in detail. Different model systems are presented such as the different bulk phases of ice and various adsorbed monolayer structures on metal surfaces.

Abstract: We perform a low-mass dark matter search using an exposure of 30 kg$\times$yr with the XENON100 detector. By dropping the requirement of a scintillation signal and using only the ionization signal to determine the interaction energy, we lowered the energy threshold for detection to 0.7 keV for nuclear recoils. No dark matter detection can be claimed because a complete background model cannot be constructed without a primary scintillation signal. Instead, we compute an upper limit on the WIMP-nucleon scattering cross section under the assumption that every event passing our selection criteria could be a signal event. Using an energy interval from 0.7 keV to 9.1 keV, we derive a limit on the spin-independent WIMP-nucleon cross section that excludes WIMPs with a mass of 6 GeV/$c^2$ above $1.2 \times 10^{-41}$ cm$^2$ at 90\% confidence level.

Abstract: We determine the ionization time in tunneling ionization by an elliptically polarized light pulse relative to its maximum. This is achieved by a full quantum propagation of the electron wave function forward in time, followed by a classical backpropagation to identify tunneling parameters, in particular, the fraction of electrons that has tunneled out. We find that the ionization time is close to zero for single active electrons in helium and in hydrogen if the fraction of tunneled electrons is large. We expect our analysis to be essential to quantify ionization times for correlated electron motion.

Abstract: Semiclassical simulations of spectrum and dynamics of complex molecules require statistical sampling of coordinates and momenta. The effects of using thermal and quantum samplings are analyzed taking pyrrole as a test case. It is shown that there are significant differences in the results obtained with each of these two approaches. Overall, quantum sampling based on a Wigner distribution renders superior results, comparing well to the experiments. Dynamics simulations based on surface hopping and ADC(2) reveal that pyrrole internal conversion to the ground state occurs not only through H-elimination path, but also through ring-distortion paths, which have been systematically neglected by diverse experimental setups. The analysis of the reaction paths also shows that the ionization potential varies by more than 5 eV between ionization of the excited state at the Franck-Condon region and at the intersections with the ground state. This feature may have major implications for time-resolved photoelectron spectroscopy. (c) 2015 Wiley Periodicals, Inc.

Abstract: Any injection of electromagnetically interacting particles during the cosmic dark ages will lead to increased ionization, heating, production of Lyman-$\ensuremath{\alpha}$ photons and distortions to the energy spectrum of the cosmic microwave background, with potentially observable consequences. In this paper we describe numerical results for the low-energy electrons and photons produced by the cooling of particles injected at energies from keV to multi-TeV scales, at arbitrary injection redshifts (but focusing on the post-recombination epoch). We use these data, combined with existing calculations modeling the cooling of these low-energy particles, to estimate the resulting contributions to ionization, excitation and heating of the gas, and production of low-energy photons below the threshold for excitation and ionization. We compute corrected deposition-efficiency curves for annihilating dark matter, and demonstrate how to compute equivalent curves for arbitrary energy-injection histories. These calculations provide the necessary inputs for the limits on dark matter annihilation presented in the accompanying paper I, but also have potential applications in the context of dark matter decay or deexcitation, decay of other metastable species, or similar energy injections from new physics. We make our full results publicly available at http://nebel.rc.fas.harvard.edu/epsilon, to facilitate further independent studies. In particular, we provide the full low-energy electron and photon spectra, to allow matching onto more detailed codes that describe the cooling of such particles at low energies.

Abstract: Energetic particle precipitation (EPP) and ion chemistry affect the neutral composition of the polar middle atmosphere. For example, production of odd nitrogen and odd hydrogen during strong events can decrease ozone by tens of percent. However, the standard ion chemistry parameterization used in atmospheric models neglects the effects on some important species, such as nitric acid. We present WACCM-D, a variant of the Whole Atmosphere Community Climate Model, which includes a set of lower ionosphere (D-region) chemistry: 307 reactions of 20 positive ions and 21 negative ions. We consider realistic ionization scenarios and compare the WACCM-D results to those from the Sodankyla Ion and Neutral Chemistry (SIC), a state-of-the-art 1-D model of the D-region chemistry. We show that WACCM-D produces well the main characteristics of the D-region ionosphere, as well as the overall proportion of important ion groups, in agreement with SIC. Comparison of ion concentrations shows that the WACCM-D bias is typically within ±10% or less below 70 km. At 70–90 km, when strong altitude gradients in ionization rates and/or ion concentrations exist, the bias can be larger for some groups but is still within tens of percent. Based on the good agreement overall and the fact that part of the differences are caused by different model setups, WACCM-D provides a state-of-the-art global representation of D-region ion chemistry and is therefore expected to improve EPP modeling considerably. These improvements are demonstrated in a companion paper by Andersson et al.

Abstract: Purpose: Magnetic resonance imaging–guided radiotherapy (MRIgRT) provides superior soft-tissue contrast and real-time imaging compared with standard image-guided RT, which uses x-ray based imaging. Several groups are developing integrated MRIgRT machines. Reference dosimetry with these new machines requires accounting for the effects of the magnetic field on the response of the ionization chambers used for dose calibration. Here, the authors propose a formalism for reference dosimetry with integrated MRIgRT devices. The authors also examined the suitability of the TPR 10 20 and %dd(10)x beam quality specifiers in the presence of magnetic fields and calculated detector correction factors to account for the effects of the magnetic field for a range of detectors. Methods: The authors used full-head and point-source Monte Carlo models of an MR-linac along with detailed detector models of an Exradin A19, an NE2571, and several PTW Farmer chambers to calculate magnetic field correction factors for six commercial ionization chambers in three chamber configurations. Calculations of ionization chamber response (performed with geant4) were validated with specialized Fano cavity tests. %dd(10)x values, TPR 10 20 values, and Spencer-Attix water-to-air restricted stopping power ratios were also calculated. The results were further validated against measurements made with a preclinical functioning MR-linac. Results: The TPR 10 20 was found to be insensitive to the presence of the magnetic field, whereas the relative change in %dd(10)x was 2.4% when a transverse 1.5 T field was applied. The parameters chosen for the ionization chamber calculations passed the Fano cavity test to within ∼0.1%. Magnetic field correction factors varied in magnitude with detector orientation with the smallest corrections found when the chamber was parallel to the magnetic field. Conclusions: Reference dosimetry can be performed with integrated MRIgRT devices by using magnetic field correction factors, but care must be taken with the choice of beam quality specifier and chamber orientation. The uncertainties achievable under this formalism should be similar to those of conventional formalisms, although this must be further quantified.

Abstract: The Orion Bar is the archetypal edge-on molecular cloud surface illuminated by strong ultraviolet radiation from nearby massive stars. Owing to the close distance to Orion (about 1,350 light-year), the effects of stellar feedback on the parental cloud can be studied in detail. Visible-light observations of the Bar(1) show that the transition between the hot ionised gas and the warm neutral atomic gas (the ionisation front) is spatially well separated from the transition from atomic to molecular gas (the dissociation front): about 15 arcseconds or 6,200 astronomical units (one astronomical unit is the Earth-Sun distance). Static equilibrium models(2,3) used to interpret previous far-infrared and radio observations of the neutral gas in the Bar(4,5,6) (typically at 10-20 arcsecond resolution) predict an inhomogeneous cloud structure consisting of dense clumps embedded in a lower density extended gas component. Here we report one-arcsecond-resolution millimetre-wave images that allow us to resolve the molecular cloud surface. In contrast to stationary model predictions(7,8,9), there is no appreciable offset between the peak of the H2 vibrational emission (delineating the H/H2 transition) and the edge of the observed CO and HCO+ emission. This implies that the H/H2 and C+/C/CO transition zones are very close. These observations reveal a fragmented ridge of high-density substructures, photoablative gas flows and instabilities at the molecular cloud surface. The results suggest that the cloud edge has been compressed by a high-pressure wave that currently moves into the molecular cloud. The images demonstrate that dynamical and nonequilibrium effects are important for the cloud evolution.

Abstract: We present a semiclassical two-step model for strong-field ionization that accounts for path interferences of tunnel-ionized electrons in the ionic potential beyond perturbation theory. Within the framework of a classical trajectory Monte Carlo representation of the phase-space dynamics, the model employs the semiclassical approximation to the phase of the full quantum propagator in the exit channel. By comparison with the exact numerical solution of the time-dependent Schr\"odinger equation for strong-field ionization of hydrogen, we show that for suitable choices of the momentum distribution after the first tunneling step, the model yields good quantitative agreement with the full quantum simulation. The two-dimensional photoelectron momentum distributions, the energy spectra, and the angular distributions are found to be in good agreement with the corresponding quantum results. Specifically, the model quantitatively reproduces the fanlike interference patterns in the low-energy part of the two-dimensional momentum distributions, as well as the modulations in the photoelectron angular distributions.

Abstract: Electron dynamics induced by resonant absorption of light is of fundamental importance in nature and has been the subject of countless studies in many scientific areas. Above the ionization threshold of atomic or molecular systems, the presence of discrete states leads to autoionization, which is an interference between two quantum paths: direct ionization and excitation of the discrete state coupled to the continuum. Traditionally studied with synchrotron radiation, the probability for autoionization exhibits a universal Fano intensity profile as a function of excitation energy. However, without additional phase information, the full temporal dynamics cannot be recovered. Here we use tunable attosecond pulses combined with weak infrared radiation in an interferometric setup to measure not only the intensity but also the phase variation of the photoionization amplitude across an autoionization resonance in argon. The phase variation can be used as a fingerprint of the interactions between the discrete state and the ionization continua, indicating a new route towards monitoring electron correlations in time.

Abstract: We study the relationship between stellar mass, star formation rate (SFR),ionization state, and gas-phase metallicity for a sample of 41 normal star-forming galaxies at $3 \lesssim z \lesssim 3.7$. The gas-phase oxygen abundance, ionization parameter, and electron density of ionized gas are derived from rest-frame optical strong emission lines measured on near-infrared spectra obtained with Keck/MOSFIRE. We remove the effect of these strong emission lines in the broad-band fluxes to compute stellar masses via spectral energy distribution fitting, while the SFR is derived from the dust-corrected ultraviolet luminosity. The ionization parameter is weakly correlated with the specific SFR, but otherwise the ionization parameter and electron density do not correlate with other global galaxy properties such as stellar mass, SFR, and metallicity. The mass-metallicity relation (MZR) at $z\simeq3.3$ shows lower metallicity by $\simeq 0.7$ dex than that at $z=0$ at the same stellar mass. Our sample shows an offset by $\simeq 0.3$ dex from the locally defined mass-metallicity-SFR relation, indicating that simply extrapolating such relation to higher redshift may predict an incorrect evolution of MZR. Furthermore, within the uncertainties we find no SFR-metallicity correlation, suggesting a less important role of SFR in controlling the metallicity at high redshift. We finally investigate the redshift evolution of the MZR by using the model by Lilly et al. (2013), finding that the observed evolution from $z=0$ to $z\simeq3.3$ can be accounted for by the model assuming a weak redshift evolution of the star formation efficiency.

Abstract: We study the relationship between stellar mass, star formation rate (SFR), ionization state, and gas-phase metallicity for a sample of 41 normal star-forming galaxies at 3 ≾ z ≾ 3.7. The gas-phase oxygen abundance, ionization parameter, and electron density of ionized gas are derived from rest-frame optical strong emission lines measured on near-infrared spectra obtained with Keck/Multi-Object Spectrograph for Infra-Red Exploration. We remove the effect of these strong emission lines in the broadband fluxes to compute stellar masses via spectral energy distribution fitting, while the SFR is derived from the dust-corrected ultraviolet luminosity. The ionization parameter is weakly correlated with the specific SFR, but otherwise the ionization parameter and electron density do not correlate with other global galaxy properties such as stellar mass, SFR, and metallicity. The mass–metallicity relation (MZR) at z ≃ 3.3 shows lower metallicity by ≃ 0.7 dex than that at z = 0 at the same stellar mass. Our sample shows an offset by ≃ 0.3 dex from the locally defined mass–metallicity–SFR relation, indicating that simply extrapolating such a relation to higher redshift may predict an incorrect evolution of MZR. Furthermore, within the uncertainties we find no SFR–metallicity correlation, suggesting a less important role of SFR in controlling the metallicity at high redshift. We finally investigate the redshift evolution of the MZR by using the model by Lilly et al., finding that the observed evolution from z = 0 to z ≃ 3.3 can be accounted for by the model assuming a weak redshift evolution of the star formation efficiency.

Abstract: We investigate how photoionization, electron avalanches and space charge affect the inception of nanosecond pulsed discharges. Simulations are performed with a 3D PIC-MCC (particle-in-cell, Monte Carlo collision) model with adaptive mesh refinement for the field solver. This model, whose source code is available online, is described in the first part of the paper. Then we present simulation results in a needle-to-plane geometry, using different nitrogen/oxygen mixtures at atmospheric pressure. In these mixtures non-local photoionization is important for the discharge growth. The typical length scale for this process depends on the oxygen concentration. With 0.2% oxygen the discharges grow quite irregularly, due to the limited supply of free electrons around them. With 2% or more oxygen the development is much smoother. An almost spherical ionized region can form around the electrode tip, which increases in size with the electrode voltage. Eventually this inception cloud destabilizes into streamer channels. In our simulations, discharge velocities are almost independent of the oxygen concentration. We discuss the physical mechanisms behind these phenomena and compare our simulations with experimental observations.

Abstract: We report on nonsequential double ionization of Ar by a laser pulse consisting of two counterrotating circularly polarized fields (390 and 780 nm). The double-ionization probability depends strongly on the relative intensity of the two fields and shows a kneelike structure as a function of intensity. We conclude that double ionization is driven by a beam of nearly monoenergetic recolliding electrons, which can be controlled in intensity and energy by the field parameters. The electron momentum distributions show the recolliding electron as well as a second electron which escapes from an intermediate excited state of Ar^{+}.

Abstract: A new reactive ionization region model (R-IRM) is developed to describe the reactive Ar/O-2 high power impulse magnetron sputtering (HiPIMS) discharge with a titanium target. It is then applied to ...

Abstract: Atoms undergoing strong-field ionization in two-color circularly polarized femtosecond laser fields exhibit unique two-dimensional photoelectron trajectories and can emit bright circularly polarized extreme ultraviolet and soft-x-ray beams. In this Letter, we present the first experimental observation of nonsequential double ionization in these tailored laser fields. Moreover, we can enhance or suppress nonsequential double ionization by changing the intensity ratio and helicity of the two driving laser fields to maximize or minimize high-energy electron-ion rescattering. Our experimental results are explained through classical simulations, which also provide insight into how to optimize the generation of circularly polarized high harmonic beams.

Abstract: We report a new strategy for the direct coupling of Solid-Phase Microextraction (SPME) with mass spectrometry, based on thermal desorption of analytes extracted on the fibers, followed by ionization by a dielectric barrier discharge ionization (DBDI) source. Limits of detection as low as 0.3 pg/mL and a linear dynamic range of ≥3 orders of magnitude were achieved, with a very simple and reproducible approach. Different from direct analysis in real time (DART), desorption electrospray ionization (DESI), or low-temperature plasma (LTP), the desorption of the analytes from the SPME devices in our setup is completely separated from the ionization event. This enhances the reproducibility of the method and minimizes ion suppression phenomena. The analytes were quantitatively transferred from the SPME to the DBDI source, and the use of an active capillary ionization embodiment of the DBDI source greatly enhanced the ion transmission to the MS. This, together with the extraordinary sensitivity of DBDI, allowed su...

Abstract: Mass spectrometry imaging (MSI) is a comprehensive tool for the analysis of a wide range of biomolecules. The mainstream method for molecular MSI is matrix-assisted laser desorption ionization, however, the presence of a matrix results in spectral interferences and the suppression of some analyte ions. Herein we demonstrate a new matrix-free MSI technique using nanophotonic ionization based on laser desorption ionization (LDI) from a highly uniform silicon nanopost array (NAPA). In mouse brain and kidney tissue sections, the distributions of over 80 putatively annotated molecular species are determined with 40 μm spatial resolution. Furthermore, NAPA-LDI-MS is used to selectively analyze metabolites and lipids from sparsely distributed algal cells and the lamellipodia of human hepatocytes. Our results open the door for matrix-free MSI of tissue sections and small cell populations by nanophotonic ionization.

Abstract: A theory of above-threshold ionization of atoms by a strong laser field is formulated. Two versions of the strong-field approximation (SFA) are considered, the direct SFA and the improved SFA, which do not and do, respectively, take into account rescattering of the freed electron off the parent ion. The atomic bound state is included in two different ways: as an expansion in terms of Slater-type orbitals or as an asymptotic wave function. Even though we are using the single-active-electron approximation, multielectron effects are taken into account in two ways: by a proper choice of the ground state and by an adequate definition of the ionization rate. For the case of the asymptotic bound-state wave functions, using the saddle-point method, a simple expression for the $T$-matrix element is derived for both the direct and the improved SFA. The theory is applied to ionization by a bicircular field, which consists of two coplanar counterrotating circularly polarized components with frequencies that are integer multiples of a fundamental frequency $\ensuremath{\omega}$. Special emphasis is on the $\ensuremath{\omega}\text{\ensuremath{-}}2\ensuremath{\omega}$ case. In this case, the threefold rotational symmetry of the field carries over to the velocity map of the liberated electrons, for both the direct and the improved SFA. The results obtained are analyzed in detail using the quantum-orbit formalism, which gives good physical insight into the above-threshold ionization process. For this purpose, a specific classification of the saddle-point solutions is introduced for both the backward-scattered and the forward-scattered electrons. The high-energy backward-scattering quantum orbits are similar to those discovered for high-order harmonic generation. The short forward-scattering quantum orbits for a bicircular field are similar to those of a linearly polarized field. The conclusion is that these orbits are universal, i.e., they do not depend much on the shape of the laser field.

Abstract: . Proton transfer reactions between hydronium ions (H3O+) and volatile organic compounds (VOCs) provide a fast and highly sensitive technique for VOC measurements, leading to extensive use of proton-transfer-reaction mass spectrometry (PTR-MS) in atmospheric research. Based on the same ionization approach, we describe the development of a high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) utilizing H3O+ as the reagent ion. The new H3O+ ToF-CIMS has sensitivities of 100–1000 cps ppb−1 (ion counts per second per part-per-billion mixing ratio of VOC) and detection limits of 20–600 ppt at 3σ for a 1 s integration time for simultaneous measurements of many VOC species of atmospheric relevance. The ToF analyzer with mass resolution (m∕Δm) of up to 6000 allows the separation of isobaric masses, as shown in previous studies using similar ToF-MS. While radio frequency (RF)-only quadrupole ion guides provide better overall ion transmission than ion lens system, low-mass cutoff of RF-only quadrupole causes H3O+ ions to be transmitted less efficiently than heavier masses, which leads to unusual humidity dependence of reagent ions and difficulty obtaining a humidity-independent parameter for normalization. The humidity dependence of the instrument was characterized for various VOC species and the behaviors for different species can be explained by compound-specific properties that affect the ion chemistry (e.g., proton affinity and dipole moment). The new H3O+ ToF-CIMS was successfully deployed on the NOAA WP-3D research aircraft for the SONGNEX campaign in spring of 2015. The measured mixing ratios of several aromatics from the H3O+ ToF-CIMS agreed within ±10 % with independent gas chromatography measurements from whole air samples. Initial results from the SONGNEX measurements demonstrate that the H3O+ ToF-CIMS data set will be valuable for the identification and characterization of emissions from various sources, investigation of secondary formation of many photochemical organic products and therefore the chemical evolution of gas-phase organic carbon in the atmosphere.