Abstract: This review focuses on one of the fundamental phenomena that occur upon application of sufficiently strong electric fields to gases, namely the formation and propagation of ionization waves-streamers. The dynamics of streamers is controlled by strongly nonlinear coupling, in localized streamer tip regions, between enhanced (due to charge separation) electric field and ionization and transport of charged species in the enhanced field. Streamers appear in nature (as initial stages of sparks and lightning, as huge structures-sprites above thunderclouds), and are also found in numerous technological applications of electrical discharges. Here we discuss the fundamental physics of the guided streamer-like structures-plasma bullets which are produced in cold atmospheric-pressure plasma jets. Plasma bullets are guided ionization waves moving in a thin column of a jet of plasma forming gases (e.g.,He or Ar) expanding into ambient air. In contrast to streamers in a free (unbounded) space that propagate in a stochastic manner and often branch, guided ionization waves are repetitive and highly-reproducible and propagate along the same path-the jet axis. This property of guided streamers, in comparison with streamers in a free space, enables many advanced time-resolved experimental studies of ionization waves with nanosecond precision. In particular, experimental studies on manipulation of streamers by external electric fields and streamer interactions are critically examined. This review also introduces the basic theories and recent advances on the experimental and computational studies of guided streamers, in particular related to the propagation dynamics of ionization waves and the various parameters of relevance to plasma streamers. This knowledge is very useful to optimize the efficacy of applications of plasma streamer discharges in various fields ranging from health care and medicine to materials science and nanotechnology.

Abstract: A high-resolution time-of-flight chemical-ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adducts has been characterized and deployed in several laboratory and field studies to measure a suite of organic and inorganic atmospheric species. The large negative mass defect of Iodide, combined with soft ionization and the high mass-accuracy ( 5500) of the time-of-flight mass spectrometer, provides an additional degree of separation and allows for the determination of elemental compositions for the vast majority of detected ions. Laboratory characterization reveals Iodide-adduct ionization generally exhibits increasing sensitivity toward more polar or acidic volatile organic compounds. Simultaneous retrieval of a wide range of mass-to-charge ratios (m/Q from 25 to 625 Th) at a high frequency (>1 Hz) provides a comprehensive view of atmospheric oxidative chemistry, particularly when sampling rapidly evolving plumes from fast moving platforms like an aircraft. We pres...

Abstract: Direct analysis in real time mass spectrometry (DART-MS) has become an established technique for rapid mass spectral analysis of a large variety of samples. DART-MS is capable of analyzing the sample at atmospheric pressure, essentially in the open laboratory environment. DART-MS can be applied to compounds that have been deposited or adsorbed on to surfaces or that are being desorbed therefrom into the atmosphere. This makes DART-MS suitable and well-known for analysis of ingredients of plant materials, pesticide monitoring on vegetables, forensic and safety applications such as screening for traces of explosives, warfare agents, or illicit drugs on luggage, clothes, or bank notes, etc. DART can also be used for analysis of either solid or liquid bulk materials, as may be required in quality control, or to quickly investigate the identity of a compound from chemical synthesis. Even living organisms can be subjected to DART-MS. Driven by different needs in analytical practice, the combination of the DART ionization source and interface can be configured in multiple geometries and with various accessories to adapt the setup as required. Analysis by DART-MS relies on some sort of gas-phase ionization mechanism. In DART, initial generation of the ionizing species is by use of a corona discharge in a pure helium atmosphere which delivers excited helium atoms that, upon their release into the atmosphere, will initiate a cascade of gas-phase reactions. In the end, this results in reagent ions created from atmospheric water or (solvent) vapor in the vicinity of the surface subject to analysis where they effect a chemical ionization process. DART ionization processes may generate positive or negative ions, predominantly even-electron species, but odd-electron species do also occur. The prevailing process of analyte ion formation from a given sample is highly dependent on analyte properties.

Abstract: The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3–)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the...

Abstract: The ionization potential is a fundamental key quantity with great relevance to diverse material properties. We find that state of the art methods based on density functional theory and simple diagrammatic approaches as commonly taken in the GW approximation predict the ionization potentials of semiconductors and insulators unsatisfactorily. Good agreement between theory and experiment is obtained only when diagrams resulting from the antisymmetry of the many-electron wave function are taken into account via vertex corrections in the self-energy. The present approach describes both localized and delocalized states accurately, making it ideally suited for a wide class of materials and processes.

Abstract: We use a zero-dimensional reaction kinetics model to simulate CO2 conversion in microwave discharges where the excitation of the vibrational levels plays a significant role in the dissociation kinetics. The model includes a description of the CO2 vibrational kinetics, taking into account state-specific VT and VV relaxation reactions and the effect of vibrational excitation on other chemical reactions. The model is used to simulate a general tubular microwave reactor, where a stream of CO2 flows through a plasma column generated by microwave radiation. We study the effects of the internal plasma parameters, namely the reduced electric field, electron density and the total specific energy input, on the CO2 conversion and its energy efficiency. We report the highest energy efficiency (up to 30%) for a specific energy input in the range 0.4–1.0 eV/molecule and a reduced electric field in the range 50–100 Td and for high values of the electron density (an ionization degree greater than 10−5). The energy efficiency is mainly limited by the VT relaxation which contributes dominantly to the vibrational energy losses and also contributes significantly to the heating of the reacting gas. The model analysis provides useful insight into the potential and limitations of CO2 conversion in microwave discharges.

Abstract: We report the breakdown of the electric dipole approximation in the long-wavelength limit in strong-field ionization with linearly polarized few-cycle mid-infrared laser pulses at intensities on the order of 10¹³ W/cm². Photoelectron momentum distributions were recorded by velocity map imaging and projected onto the beam propagation axis. We observe an increasing shift of the peak of this projection opposite to the beam propagation direction with increasing laser intensities. From a comparison with semiclassical simulations, we identify the combined action of the magnetic field of the laser pulse and the Coulomb potential as the origin of our observations.

Abstract: This work addresses the effect of energy level alignment between the hole-transporting material and the active layer in vacuum deposited, planar-heterojunction CH3NH3PbIx−3Clx perovskite solar cells. Through a series of hole-transport materials, with conductivity values set using controlled p-doping of the layer, we correlate their ionization potentials with the open-circuit voltage of the device. With ionization potentials beyond 5.3 eV, a substantial decrease in both current density and voltage is observed, which highlights the delicate energetic balance between driving force for hole-extraction and maximizing the photovoltage. In contrast, when an optimal ionization potential match is found, the open-circuit voltage can be maximized, leading to power conversion efficiencies of up to 10.9%. These values are obtained with hole-transport materials that differ from the commonly used Spiro-MeO-TAD and correspond to a 40% performance increase versus this reference.

Abstract: Resolving in time the dynamics of light absorption by atoms and molecules, and the electronic rearrangement this induces, is among the most challenging goals of attosecond spectroscopy. The attoclock is an elegant approach to this problem, which encodes ionization times in the strong-field regime. However, the accurate reconstruction of these times from experimental data presents a formidable theoretical challenge. Here, we solve this problem by combining analytical theory with ab-initio numerical simulations. We apply our theory to numerical attoclock experiments on the hydrogen atom to extract ionization time delays and analyse their nature. Strong field ionization is often viewed as optical tunnelling through the barrier created by the field and the core potential. We show that, in the hydrogen atom, optical tunnelling is instantaneous. By calibrating the attoclock using the hydrogen atom, our method opens the way to identify possible delays associated with multielectron dynamics during strong-field ionization.

Abstract: We compute a large grid of photoionization models that covers a wide range of physical parameters and is representative of most of the observed PNe. Using this grid, we derive new formulae for the ionization correction factors (ICFs) of He, O, N, Ne, S, Ar, Cl, and C. Analytical expressions to estimate the uncertainties arising from our ICFs are also provided. This should be useful since these uncertainties are usually not considered when estimating the error bars in element abundances. Our ICFs are valid over a variety of assumptions such as the input metallicities, the spectral energy distribution of the ionizing source, the gas distribution, or the presence of dust grains. Besides, the ICFs are adequate both for large aperture observations and for pencil-beam observations in the central zones of the nebulae. We test our ICFs on a large sample of observed PNe that extends as far as possible in ionization, central star temperature, and metallicity, by checking that the Ne/O, S/O, Ar/O, and Cl/O ratios show no trend with the degree of ionization. Our ICFs lead to significant differences in the derived abundance ratios as compared with previous determinations, especially for N/O, Ne/O, and Ar/O.

Abstract: An analysis is presented of measured and calculated cross sections for inner-shell ionization by electron impact. We describe the essentials of classical and semiclassical models and of quantum approximations for computing ionization cross sections. The emphasis is on the recent formulation of the distorted-wave Born approximation by Bote and Salvat [Phys. Rev. A 77, 042701 (2008)] that has been used to generate an extensive database of cross sections for the ionization of the K shell and the L and M subshells of all elements from hydrogen to einsteinium (Z = 1 to Z = 99) by electrons and positrons with kinetic energies up to 1 GeV. We describe a systematic method for evaluating cross sections for emission of x rays and Auger electrons based on atomic transition probabilities from the Evaluated Atomic Data Library of Perkins et al. [Lawrence Livermore National Laboratory, UCRL-ID-50400, 1991]. We made an extensive comparison of measured K-shell, L-subshell, and M-subshell ionization cross sections and of ...

Abstract: Intermolecular Coulombic decay driven by resonant Auger decay can be used to produce low-energy electrons selectively from chosen molecular or atomic sites and with tunable energies, with possible applications in radiation therapy. The irradiation of matter with light tends to electronically excite atoms and molecules. What happens to the resulting excitation energy depends on the nature of the relaxation pathway and the energy of the electrons and ions produced. In one such pathway, known as intermolecular Coulombic decay (ICD), excess energy is transferred to neighbouring atoms or molecules that then lose an electron and become ionized. ICD electrons have relatively low energy, prompting suggestions that they might be harnessed as a form of Auger therapy — cancer treatment that uses large numbers of genotoxic low-energy electrons to damage cancer cells. In a pair of papers [in this issue of Nature] published online this week, Gokhberg et al. propose that ICD can be triggered upon relaxation of an initial resonant core excitation, and Trinter et al. confirm the existence of the proposed excitation experimentally. The efficiency of this relaxation cascade and the fact that it can be tuned to directly control the generation site and the energy of the electrons raise the prospect of the development of more targeted cancer radiotherapy, and possibly new spectroscopic techniques. Irradiation of matter with light tends to electronically excite atoms and molecules, with subsequent relaxation processes determining where the photon energy is ultimately deposited and electrons and ions produced. In weakly bound systems, intermolecular Coulombic decay1 (ICD) enables very efficient relaxation of electronic excitation through transfer of the excess energy to neighbouring atoms or molecules that then lose an electron and become ionized2,3,4,5,6,7,8,9. Here we propose that the emission site and energy of the electrons released during this process can be controlled by coupling the ICD to a resonant core excitation. We illustrate this concept with ab initio many-body calculations on the argon–krypton model system, where resonant photoabsorption produces an initial or ‘parent’ excitation of the argon atom, which then triggers a resonant-Auger-ICD cascade that ends with the emission of a slow electron from the krypton atom. Our calculations show that the energy of the emitted electrons depends sensitively on the initial excited state of the argon atom. The incident energy can thus be adjusted both to produce the initial excitation in a chosen atom and to realize an excitation that will result in the emission of ICD electrons with desired energies. These properties of the decay cascade might have consequences for fundamental and applied radiation biology and could be of interest in the development of new spectroscopic techniques.

Abstract: Experimentally, the bound and dissociative nuclear dynamics in small molecular ions can be resolved in time by using intense ultrashort pump in combination with delayed probe laser pulses. We discuss the modelling of related pump–probe-delay-dependent fragment kinetic-energy-release (KER) spectra for the laser-induced dissociative ionization of selected diatomic molecules and show how the quantum-mechanical simulation of measured KER spectra—in both the time domain and as a function of the beat frequency between molecular vibrational levels—reveals dissociation pathways and the characteristics of initially occupied molecular potential curves.

Abstract: The origin of turbulence in accretion discs is still not fully understood. While the magneto-rotational instability is considered to operate in sufficiently ionized discs, its role in the poorly ionized protoplanetary disc is questionable. Recently, the vertical shear instability (VSI) has been suggested as a possible alternative. Our goal is to study the characteristics of this instability and the efficiency of angular momentum transport, in extended discs, under the influence of radiative transport and irradiation from the central star. We use multi-dimensional hydrodynamic simulations to model a larger section of an accretion disc. First we study inviscid and weakly viscous discs using a fixed radial temperature profile in two and three spatial dimensions. The simulations are then extended to include radiative transport and irradiation from the central star. In agreement with previous studies we find for the isothermal disc a sustained unstable state with a weak positive angular momentum transport of the order of $\alpha \approx 10^{-4}$. Under the inclusion of radiative transport the disc cools off and the turbulence terminates. For discs irradiated from the central star we find again a persistent instability with a similar $\alpha$ value as for the isothermal case. We find that the VSI can indeed generate sustained turbulence in discs albeit at a relatively low level with $\alpha$ about few times $10^{-4}$

Abstract: We investigate the roles of magnetic fields and ambipolar diffusion during prestellar core formation in turbulent giant molecular clouds, using three-dimensional numerical simulations. Our simulations focus on the shocked layer produced by a converging large-scale flow and survey varying ionization and the angle between the upstream flow and magnetic field. We also include ideal magnetohydrodynamic (MHD) and hydrodynamic models. From our simulations, we identify hundreds of self-gravitating cores that form within 1 Myr, with masses M ~ 0.04-2.5 M ☉ and sizes L ~ 0.015-0.07 pc, consistent with observations of the peak of the core mass function. Median values are M = 0.47 M ☉ and L = 0.03 pc. Core masses and sizes do not depend on either the ionization or upstream magnetic field direction. In contrast, the mass-to-flux ratio does increase with lower ionization, from twice to four times the critical value. The higher mass-to-flux ratio for low ionization is the result of enhanced transient ambipolar diffusion when the shocked layer first forms. However, ambipolar diffusion is not necessary to form low-mass supercritical cores. For ideal MHD, we find similar masses to other cases. These masses are one to two orders of magnitude lower than the value M mag, sph = 0.007B 3/(G 3/2ρ2) that defines a magnetically supercritical sphere under post-shock ambient conditions. This discrepancy is the result of anisotropic contraction along field lines, which is clearly evident in both ideal MHD and diffusive simulations. We interpret our numerical findings using a simple scaling argument that suggests that gravitationally critical core masses will depend on the sound speed and mean turbulent pressure in a cloud, regardless of magnetic effects.

Abstract: We derive self-consistent formalism for the description of multi-component partially ionized solar plasma, by means of the coupled equations for the charged and neutral components for an arbitrary number of chemical species, and the radiation field. All approximations and assumptions are carefully considered. Generalized Ohm's law is derived for the single-fluid and two-fluid formalism. Our approach is analytical with some order-of-magnitude support calculations. After general equations are developed, we particularize to some frequently considered cases as for the interaction of matter and radiation.

Abstract: Electrospray ionization (ESI) in the negative ion mode has received less attention in fundamental studies than the positive ion electrospray ionization In this paper, we study the efficiency of negative ion formation in the ESI source via deprotonation of substituted phenols and benzoic acids and explore correlations of the obtained ionization efficiency values (logIE) with different molecular properties It is observed that stronger acids (ie, fully deprotonated in the droplets) yielding anions with highly delocalized charge [quantified by the weighted average positive sigma (WAPS) parameter rooted in the COSMO theory] have higher ionization efficiency and give higher signals in the negative-ion ESI/MS A linear model was obtained, which equally well describes the logIE of both phenols and benzoic acids (R2 = 083, S = 040 log units) and contains only an ionization degree in solution (α) and WAPS as molecular parameters Both parameters can easily be calculated with the COSMO-RS method The model was

Abstract: The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

Abstract: We investigate photon-momentum sharing between an electron and an ion following different photoionization regimes. We find very different partitioning of the photon momentum in one-photon ionization (the photoelectric effect) as compared to multiphoton processes. In the photoelectric effect, the electron acquires a momentum that is much greater than the single photon momentum ℏω/c [up to (8/5) ℏω/c] whereas in the strong-field ionization regime, the photoelectron only acquires the momentum corresponding to the photons absorbed above the field-free ionization threshold plus a momentum corresponding to a fraction (3/10) of the ionization potential Ip. In both cases, due to the smallness of the electron-ion mass ratio, the ion takes nearly the entire momentum of all absorbed N photons (via the electron-ion center of mass). Additionally, the ion takes, as a recoil, the photoelectron momentum resulting from mutual electron-ion interaction in the electromagnetic field. Consequently, the momentum partitioning of the photofragments is very different in both regimes. This suggests that there is a rich, unexplored physics to be studied between these two limits which can be generated with current ultrafast laser technology.

Abstract: The chemical properties of protoplanetary disks are especially sensitive to their ionization environment. Sources of molecular gas ionization include cosmic rays, stellar X-rays and short-lived radionuclides, each of which varies with location in the disk. This behavior leads to a significant amount of chemical structure, especially in molecular ion abundances, which is imprinted in their submillimeter rotational line emission. Using an observationally motivated disk model, we make predictions for the dependence of chemical abundances on the assumed properties of the ionizing field. We calculate the emergent line intensity for abundant molecular ions and simulate sensitive observations with the Atacama Large Millimeter/Sub-millimeter Array (ALMA) for a disk at D=100 pc. The models readily distinguish between high ionization rates ($\zeta\gtrsim10^{-17}$ s$^{-1}$ per H$_2$) and below, but it becomes difficult to distinguish between low ionization models when $\zeta\lesssim10^{-19}$ s$^{-1}$. We find that \htdp\ emission is not detectable for sub-interstellar CR rates with ALMA (6h integration), and that tdp\ emission may be a more sensitive tracer of midplane ionization. HCO$^+$ traces X-rays and high CR rates ($\zeta_{\rm{CR}}\gtrsim10^{-17}$ s$^{-1}$), and provides a handle on the warm molecular ionization properties where CO is present in the gas. Furthermore, species like HCO$^+$, which emits from a wide radial region and samples a large gradient in temperature, can exhibit ring-like emission as a consequence of low-lying rotational level de-excitation near the star. This finding highlights a scenario where rings are not necessarily structural or chemical in nature, but simply a result of the underlying line excitation properties.

Abstract: Electrospray ionization mass spectrometry (ESI-MS) is a soft ionization technique commonly coupled with liquid or gas chromatography for the identification of compounds in a one-time view of a mixture (for example, the resulting mixture generated by a synthesis). Over the past decade, Scott McIndoe and his research group at the University of Victoria have developed various methodologies to enhance the ability of ESI-MS to continuously monitor catalytic reactions as they proceed. The power, sensitivity and large dynamic range of ESI-MS have allowed for the refinement of several homogenous catalytic mechanisms and could potentially be applied to a wide range of reactions (catalytic or otherwise) for the determination of their mechanistic pathways. In this special feature article, some of the key challenges encountered and the adaptations employed to counter them are briefly reviewed.

Abstract: Ionization rates of molecules have been modeled with time-dependent configuration interaction simulations using atom centered basis sets and a complex absorbing potential. The simulations agree with accurate grid-based calculations for the ionization of hydrogen atom as a function of field strength and for charge resonance enhanced ionization of H2+ as the bond is elongated. Unlike grid-based methods, the present approach can be applied to simulate electron dynamics and ionization in multi-electron polyatomic molecules. Calculations on HCl+ and HCO+ demonstrate that these systems also show charge resonance enhanced ionization as the bonds are stretched.

Abstract: Ambient ionization is achieved by spraying from a carbon nanotube (CNT)-impregnated paper surface under the influence of small voltages (≥3 V). Organic molecules give simple high-quality mass spectra without fragmentation in the positive or negative ion modes. Conventional field ionization is ruled out, and it appears that field emission of microdroplets occurs. Microscopic examination of the CNT paper confirms that the nanoscale features at the paper surface are responsible for the high electric fields. Raman spectra imply substantial current flows in the nanotubes. The performance of this analytical method was demonstrated for a range of volatile and nonvolatile compounds and a variety of matrices.

Abstract: The chemical properties of protoplanetary disks are especially sensitive to their ionization environment. Sources of molecular gas ionization include cosmic rays (CRs), stellar X-rays, and short-lived radionuclides, each of which varies with location in the disk. This behavior leads to a significant amount of chemical structure, especially in molecular ion abundances, which is imprinted in their submillimeter rotational line emission. Using an observationally motivated disk model, we make predictions for the dependence of chemical abundances on the assumed properties of the ionizing field. We calculate the emergent line intensity for abundant molecular ions and simulate sensitive observations with the Atacama Large Millimeter/Sub-millimeter Array (ALMA) for a disk at D = 100?pc. The models readily distinguish between high ionization rates (? 10?17?s?1 per H2) and below, but it becomes difficult to distinguish between low ionization models when ? 10?19?s?1. We find that H2D+ emission is not detectable for sub-interstellar CR rates with ALMA (6h integration), and that N2D+ emission may be a more sensitive tracer of midplane ionization. HCO+ traces X-rays and high CR rates (?CR 10?17?s?1), and provides a handle on the warm molecular ionization properties where CO is present in the gas. Furthermore, species like HCO+, which emits from a wide radial region and samples a large gradient in temperature, can exhibit ring-like emission as a consequence of low-lying rotational level de-excitation near the star. This finding highlights a scenario where rings are not necessarily structural or chemical in nature, but simply a result of the underlying line excitation properties.

Abstract: We extend the recently proposed thermally-assisted-occupation density functional theory (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)] to generalized-gradient approximation (GGA) exchange-correlation density functionals. Relative to our previous TAO-LDA (i.e., the local density approximation to TAO-DFT), the resulting TAO-GGAs are significantly superior for a wide range of applications, such as thermochemistry, kinetics, and reaction energies. For noncovalent interactions, TAO-GGAs with empirical dispersion corrections are shown to yield excellent performance. Due to their computational efficiency for systems with strong static correlation effects, TAO-LDA and TAO-GGAs are applied to study the electronic properties (e.g., the singlet-triplet energy gaps, vertical ionization potentials, vertical electron affinities, fundamental gaps, and symmetrized von Neumann entropy) of acenes with different number of linearly fused benzene rings (up to 100), which is very challenging for conventional electronic structure methods. The ground states of acenes are shown to be singlets for all the chain lengths studied here. With the increase of acene length, the singlet-triplet energy gaps, vertical ionization potentials, and fundamental gaps decrease monotonically, while the vertical electron affinities and symmetrized von Neumann entropy (i.e., a measure of polyradical character) increase monotonically.

Abstract: Context. Planet-forming disks of gas and dust around young stars contain polycyclic aromatic hydrocarbons (PAHs). Aims. We aim to characterize how the charge state of PAHs can be used as a probe of flows of gas through protoplanetary gaps. In this context, our goal is to understand the PAH spectra of four transitional disks. In addition, we want to explain the observed correlation between PAH ionization (traced by the I6:2=I11:3 feature ratio) and the disk mass (traced by the 1.3 mm luminosity). Methods. We implement a model to calculate the charge state of PAHs in the Monte Carlo radiative transfer code MCMax. The emission spectra and ionization balance are calculated in the parameter space set by the properties of the star and the disk. Results. A benchmark modeling grid is presented that shows how PAH ionization and luminosity behave as a function of star and disk properties. The PAH ionization is most sensitive to ultraviolet (UV) radiation and the electron density. In optically thick disks, where the UV field is low and the electron density is high, PAHs are predominantly neutral. Ionized PAHs trace low-density optically thin disk regions where the UV field is high and the electron density is low. Such regions are characteristic of gas flows through the gaps of transitional disks. We demonstrate that fitting the PAH spectra of four transitional disks requires a contribution of ionized PAHs in “gas flows” through the gap. Conclusions. The PAH spectra of transitional disks can be understood as superpositions of neutral and ionized PAHs. For HD 97048, neutral PAHs in the optically thick disk dominate the spectrum. In the cases of HD 169142, HD 135344 B and Oph IRS 48, small amounts of ionized PAHs located in the “gas flows” through the gap are strong contributors to the total PAH luminosity. The observed trend in the sample of Herbig stars between the disk mass and PAH ionization may imply that lower-mass disks have larger gaps. Ionized PAHs in gas flows through these gaps contribute strongly to their spectra.

Abstract: We investigate the electron heating dynamics in electropositive argon and helium capacitively coupled RF discharges driven at 13.56 MHz by particle-in-cell simulations and by an analytical model. The model allows one to calculate the electric field outside the electrode sheaths, space and time resolved within the RF period. Electrons are found to be heated by strong ambipolar electric fields outside the sheath during the phase of sheath expansion in addition to classical sheath expansion heating. By tracing individual electrons we also show that ionization is primarily caused by electrons that collide with the expanding sheath edge multiple times during one phase of sheath expansion due to backscattering toward the sheath by collisions. A synergistic combination of these different heating events during one phase of sheath expansion is required to accelerate an electron to energies above the threshold for ionization. The ambipolar electric field outside the sheath is found to be time modulated due to a time modulation of the electron mean energy caused by the presence of sheath expansion heating only during one half of the RF period at a given electrode. This time modulation results in more electron heating than cooling inside the region of high electric field outside the sheath on time average. If an electric field reversal is present during sheath collapse, this time modulation and, thus, the asymmetry between the phases of sheath expansion and collapse will be enhanced. We propose that the ambipolar electron heating should be included in models describing electron heating in capacitive RF plasmas.

Abstract: In most PIC/MCC simulations of radio frequency capacitively coupled plasmas (CCPs) several simplifications are made: (i) fast neutrals are not traced, (ii) heavy particle induced excitation and ionization are neglected, (iii) secondary electron emission from boundary surfaces due to neutral particle impact is not taken into account, and (iv) the secondary electron emission coefficient is assumed to be constant, i.e. independent of the incident particle energy and the surface conditions. Here we question the validity of these simplifications under conditions typical for plasma processing applications. We study the effects of including fast neutrals and using realistic energy-dependent secondary electron emission coefficients for ions and fast neutrals in simulations of CCPs operated in argon at 13.56 MHz and at neutral gas pressures between 3 Pa and 100 Pa. We find a strong increase of the plasma density and the ion flux to the electrodes under most conditions, if these processes are included realistically in the simulation. The sheath widths are found to be significantly smaller and the simulation is found to diverge at high pressures for high voltage amplitudes in qualitative agreement with experimental findings. By switching individual processes on and off in the simulation we identify their individual effects on the ionization dynamics and plasma parameters. We conclude that fast neutrals and energy-dependent secondary electron emission coefficients must be included in simulations of CCPs in order to yield realistic results.