Toward a complete and comprehensive cross section database for electron scattering from NO using machine learning.

We review experimental and theoretical cross sections for electron scattering in nitric oxide (NO) and form a comprehensive set of plausible cross sections. To assess the accuracy and self-consistency of our set, we also review electron swarm transport coefficients in pure NO and admixtures of NO in Ar, for which we perform a multi-term Boltzmann equation analysis. We address observed discrepancies with these experimental measurements by training an artificial neural network to solve the inverse problem of unfolding the underlying electron-NO cross sections while using our initial cross section set as a base for this refinement. In this way, we refine a suitable quasielastic momentum transfer cross section, a dissociative electron attachment cross section, and a neutral dissociation cross section. We confirm that the resulting refined cross section set has an improved agreement with the experimental swarm data over that achieved with our initial set. We also use our refined database to calculate electron transport coefficients in NO, across a large range of density-reduced electric fields from 0.003 to 10 000 Td.

An improved set of electron-THFA cross sections refined through a neural network-based analysis of swarm data.

We review experimental and theoretical cross sections for electron transport in α-tetrahydrofurfuryl alcohol (THFA) and, in doing so, propose a plausible complete set. To assess the accuracy and self-consistency of our proposed set, we use the pulsed-Townsend technique to measure drift velocities, longitudinal diffusion coefficients, and effective Townsend first ionization coefficients for electron swarms in admixtures of THFA in argon, across a range of density-reduced electric fields from 1 to 450 Td. These measurements are then compared to simulated values derived from our proposed set using a multi-term solution of Boltzmann's equation. We observe discrepancies between the simulation and experiment, which we attempt to address by employing a neural network model that is trained to solve the inverse swarm problem of unfolding the cross sections underpinning our experimental swarm measurements. What results from our neural network-based analysis is a refined set of electron-THFA cross sections, which we confirm is of higher consistency with our swarm measurements than that which we initially proposed. We also use our database to calculate electron transport coefficients in pure THFA across a range of reduced electric fields from 0.001 to 10 000 Td.

A comparison of experimental and theoretical low energy positron scattering from furan.

This paper presents a joint experimental and theoretical study of positron scattering from furan. Experimental data were measured using the low energy positron beamline located at the Australian National University and cover an energy range from 1 eV to 30 eV. Cross sections were measured for total scattering, total elastic and inelastic scattering, positronium formation, and differential elastic scattering. Two theoretical approaches are presented: the Schwinger multichannel method and the independent atom method with screening corrected additivity rule. In addition, our data are compared to corresponding electron scattering results from the same target with a number of significant differences observed and discussed.

Electron scattering cross sections from nitrobenzene in the energy range 0.4-1000 eV: the role of dipole interactions in measurements and calculations.

Absolute total electron scattering cross sections (TCS) for nitrobenzene molecules with impact energies from 0.4 to 1000 eV have been measured by means of two different electron-transmission experimental arrangements. For the lower energies (0.4-250 eV) a magnetically confined electron beam system has been used, while for energies above 100 eV a linear beam transmission technique with high angular resolution allowed accurate measurements up to 1000 eV impact energy. In both cases random uncertainties were maintained below 5-8%. Systematic errors arising from the angular and energy resolution limits of each apparatus are analysed in detail and quantified with the help of our theoretical calculations. Differential elastic and integral elastic, excitation and ionisation as well as momentum transfer cross sections have been calculated, for the whole energy range considered here, by using an independent atom model in combination with the screening corrected additivity rule method including interference effects (IAM-SCARI). Due to the significant permanent dipole moment of nitrobenzene, additional differential and integral rotational excitation cross sections have been calculated in the framework of the Born approximation. If we ignore the rotational excitations, our calculated total cross section agrees well with our experimental results for impact energies above 15 eV. Additionally, they overlap at 10 eV with the low energy Schwinger Multichannel method with Pseudo Potentials (SMCPP) calculation available in the literature (L. S. Maioli and M. H. F. Bettega, J. Chem. Phys., 2017, 147, 164305). We find a broad feature in the experimental TCS at around 1.0 eV, which has been related to the formation of the NO2- anion and assigned to the π*(b1) resonance, according to previous mass spectra available in the literature. Other local maxima in the TCSs are found at 4.0 ± 0.2 and 5.0 ± 0.2 eV and are assigned to core excited resonances leading to the formation of the NO2- and O2- anions, respectively. Finally, for energies below 10 eV, differences found between the present measurements, the SMCPP calculation and our previous data for non-polar benzene have revealed the importance of accurately calculating the rotational excitation contribution to the TCS before comparing theoretical and experimental data. This comparison suggests that our dipole-Born calculation for nitrobenzene overestimates the magnitude of the rotational excitation cross sections below 10 eV.

A dynamical (e,2e) investigation into the ionization of the outermost orbitals of R-carvone.

We report an experimental and theoretical investigation into the dynamics of electron-impact ionization of R-carvone. Experimental triple differential cross sections are obtained in asymmetric coplanar kinematic conditions for the ionization of the unresolved combination of the three outermost molecular orbitals (41a-39a) of R-carvone. These cross sections are compared with theoretical cross sections calculated within a molecular 3-body distorted wave (M3DW) framework employing either a proper orientation average or orbital average to account for the random orientation of the molecule probed in the experiment. Here, we observe that the overall scattering behavior observed in the experiment is fairly well reproduced within the M3DW framework when implementing the proper average over orientations. The character of the ionized orbitals also provides some qualitative explanation for the observed scattering behavior. This represents substantial progress when trying to describe the scattering dynamics observed for larger molecules under intermediate-impact energy and asymmetric energy sharing scattering conditions.

Experimental and theoretical analysis for total electron scattering cross sections of benzene.

Measurements of the total electron scattering cross sections (TCSs) from benzene, in the impact energy range of 1-1000 eV, are presented here by combining two different experimental systems. The first utilizes a magnetically confined electron transmission beam for the lower energies (1-300 eV), while the second utilizes a linear transmission beam apparatus for the higher energies (100-1000 eV). These cross sections have also been calculated by means of two different theoretical methods, the Schwinger Multichannel with Pseudo Potential (SMCPP) procedure, employing two different approaches to account for the polarization of the target for impact energies between 0.1 and 15 eV, and the Independent Atom Model with the Screening Corrected Additivity Rule including Interference effect (IAM-SCAR+I) paradigm to cover the 10-10 000 eV impact energy range. The present results are compared with available theoretical and experimental data, with the level of accord being good in some cases and less satisfactory in others, and some predicted resonances have been identified. In particular, we found a π* shape resonance at 1.4 eV and another feature in the energy region 4.6-4.9 eV interpreted as a π* resonance (2B2g symmetry), which is a mixture of shape and a core excited resonance, as well as a Feshbach resonance at 5.87 eV associated with the 3s (a1g) Rydberg state. A Born-type formula to extrapolate TCS values for energies above 10 000 eV is also given. This study provides a complete set of TCS data, with uncertainty limits within 10%, ready to be used for modeling electron transport applications.

Electron scattering from 1-butanol at intermediate impact energies: Total cross sections.

We report experimental measurements of the absolute total cross sections (TCSs) for electron scattering from 1-butanol at impact energies in the range 80-400 eV. Those measurements were conducted by considering the attenuation of a collimated electron beam, at a given energy, through a gas cell containing 1-butanol, at a given pressure, and through application of the Beer-Lambert law to derive the required TCS. We also report theoretical results using the Independent-Atom Model with Screening Corrected Additivity Rule and Interference approach. Those results include the TCS, the elastic integral cross section (ICS), the ionization total ICS, and the sum over all excitation process ICSs with agreement at the TCS level between our measured and calculated results being encouraging.

Electronic structure and VUV photoabsorption measurements of thiophene.

The absolute photoabsorption cross sections for thiophene in the 5.0-10.7 eV range were measured using synchrotron radiation. New theoretical calculations performed at the time-dependent density functional theory level were used to qualitatively interpret the recorded photoabsorption spectrum. The calculations facilitated a re-analysis of the observed vibronic and Rydberg structures in the photoabsorption spectrum. Here a number of features have been re-assigned, while a number of other features have been assigned for the first time. This represents the most comprehensive and self-consistent assignment of the thiophene high-resolution photoabsorption spectrum to date.

An ab initio investigation for elastic and electronically inelastic electron scattering from para-benzoquinone.

We report the results of ab initio calculations for elastic scattering and also for excitation of individual electronic states of para-benzoquinone (pBQ) by the impact of low-energy electrons. The calculations for elastic scattering were performed with the Schwinger multichannel method implemented with pseudopotentials (SMCPP) in the static-exchange (SE) plus polarization (SEP) approximation for energies up to 50 eV. The assignments for the resonance spectrum obtained in this study are, in general, in good agreement with previous results available in the literature. For electronic excitation by electron impact, the SMCPP method with N energetically open electronic states (N open ), at either the static-exchange (N open ch-SE) or the static-exchange-plus-polarisation (N open ch-SEP) approximation, was employed to calculate the scattering amplitudes using a channel coupling scheme that ranges from the 1ch-SEP up to the 89ch-SE level of approximation, depending on the energy of interest. Integral cross sections (ICSs) and differential cross sections (DCSs) were obtained for incident electron energies lying between 15 eV and 50 eV. The study focuses on the influence of multichannel coupling effects for electronically inelastic processes, more specifically, on how the number of excited states included in the open-channel space impacts upon the convergence of the cross sections at intermediate and higher energies. In particular, we found that the magnitude of DCS and ICS results for electronic excitation decreases as more channels are included in the calculations. To the best of our knowledge, there are no other experimental or theoretical ICS or DCS results for excitation into individual electronic states of pBQ available in the literature between 15 and 50 eV against which we might compare the present calculations.

Total electron scattering cross sections from para-benzoquinone in the energy range 1-200 eV.

Total electron scattering cross sections, from para-benzoquinone, for impact energies ranging between 1 to 200 eV, have been obtained by measuring the attenuation of a linear electron beam under magnetic confinement conditions. Random uncertainty limits on these values have been found to be within 5%. Systematic errors, due to the axial magnetic beam conditions in combination with the acceptance angle of the detector, have been evaluated by integrating our calculated independent atom model with the screening corrected additivity rule and interference term elastic differential cross sections over that detection acceptance angle. Our previous calculations and measurements on this molecule (Jones et al., J. Chem. Phys., 2018, 148, 124312 and J. Chem. Phys., 2018, 148, 204305), have been compiled and complemented with new elastic and inelastic scattering cross section calculations in order to obtain a comprehensive cross section data base, within the considered energy range, for modelling purposes. The self-consistency of the present data set has been evaluated by simulating the electron transport of 15 eV electrons in para-benzoquinone, and comparing those results with the observed transmitted intensity distribution.

Integral elastic, vibrational-excitation, electronic-state excitation, ionization, and total cross sections for electron scattering from para-benzoquinone.

We report absolute experimental integral cross sections (ICSs) for the electron impact excitation of 6 bands (Bands 0-V) of unresolved electronic-states in para-benzoquinone, for incident electron energies between 20 and 40 eV. Absolute vibrational-excitation ICSs, for 3 composite vibrational bands (Bands I-III), are also reported in that same energy range. In addition, ICSs calculated within our independent atom model (IAM) with screening corrected additivity rule (SCAR) formalism, extended to account for interference (I) terms that arise due to the multi-centre nature of the scattering problem, are also reported. The sum of those ICSs gives the IAM-SCAR+I total cross section (TCS) for electron-para-benzoquinone scattering. Where possible, those calculated IAM-SCAR+I ICSs are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, we also present results from our Schwinger multichannel method with pseudopotential (SMCPP) calculations. Here elastic ICSs and ICSs corresponding to the Bands 0-III of unresolved electronic-states are presented, with agreement between the SMCPP electronic-state ICSs and those from our measurements being in good qualitative accord. The energy range of our SMCPP computations is 16-50 eV. Using the binary-encounter-Bethe (BEB) approach, total ionization cross sections for this collision system were computed. Those total ionization cross sections were then added to our SMCPP ICS results, to derive SMCPP/BEB TCSs that are typically in very good accord with those from our IAM-SCAR+I approach.

Positron scattering from pyridine.

We present a range of cross section measurements for the low-energy scattering of positrons from pyridine, for incident positron energies of less than 20 eV, as well as the independent atom model with the screening corrected additivity rule including interference effects calculation, of positron scattering from pyridine, with dipole rotational excitations accounted for using the Born approximation. Comparisons are made between the experimental measurements and theoretical calculations. For the positronium formation cross section, we also compare with results from a recent empirical model. In general, quite good agreement is seen between the calculations and measurements although some discrepancies remain which may require further investigation. It is hoped that the present study will stimulate development of ab initio level theoretical methods to be applied to this important scattering system.

Electron-impact electronic-state excitation of para-benzoquinone.

Angle resolved electron energy loss spectra (EELS) for para-benzoquinone (C6H4O2) have been recorded for incident electron energies of 20, 30, and 40 eV. Measured differential cross sections (DCSs) for electronic band features, composed of a combination of energetically unresolved electronic states, are subsequently derived from those EELS. Where possible, the obtained DCSs are compared with those calculated using the Schwinger multichannel method with pseudopotentials. These calculations were performed using a minimum orbital basis single configuration interaction framework at the static exchange plus polarisation level. Here, quite reasonable agreement between the experimental cross sections and the theoretical cross sections for the summation of unresolved states was observed.

Total cross section measurements for electron scattering from dichloromethane.

Using our magnetically confined electron transmission apparatus, we report the results of total cross sections (TCSs) for electron scattering from dichloromethane (CH2Cl2). The energy range of this study is 1-300 eV. Wherever possible, the present data are compared to earlier measured TCSs of Wan et al. [J. Chem. Phys. 94, 1865 (1991)] and Karwasz et al. [Phys. Rev. A 59, 1341 (1999)] and to the corresponding theoretical independent atom model with screening corrected additivity rule and interference term (IAM-SCAR+I) results of Krupa et al. [Phys. Rev. A 97, 042702 (2018)] and a spherical complex optical potential formulation calculation of Naghma et al. [J. Electron Spectrosc. Relat. Phenom. 193, 48 (2014)]. Within their respective uncertainties, the present TCS and those of Karwasz et al. are found to be in very good agreement over their common energy range. However, agreement with the results of Wan et al. is quite poor. The importance of the experimentally inherent 'missing angle' effect (see later) on the measured TCS is investigated and found to be significant at the lower energies studied. Indeed, when this effect is accounted for, agreement between our measured TCSs and the corrected IAM-SCAR+I+rotations calculation results are, for energies above about 3 eV, in good accord (to better than 8%). Finally, we observe two σ * shape resonances, consistent with the earlier electron transmission spectroscopy results of Burrow et al. [J. Chem. Phys. 77, 2699 (1982)], at about 2.8 eV and 4.4 eV incident electron energy, in our measured TCS.

Self-consistency of electron-THF cross sections using electron swarm techniques.

The drift velocity and first Townsend ionization coefficient of electrons in gaseous tetrahydrofuran are measured over the range of reduced electric fields 4-1000 Td using a pulsed-Townsend technique. The measured drift velocities and Townsend ionization coefficients are subsequently used, in conjunction with a multi-term Boltzmann equation analysis, as a further discriminative assessment on the accuracy and completeness of a recently proposed set of electron-THF vapor cross sections. In addition, the sensitivity of the transport coefficients to uncertainties in the existing cross sections is presented. As a result of that analysis, a refinement of the momentum transfer cross section for electron-THF scattering is presented, along with modifications to the neutral dissociation and dissociative electron attachment cross sections. With these changes to the cross section database, we find relatively good self-consistency between the measured and simulated drift velocities and Townsend coefficients.

Total cross sections for electron scattering by 1-propanol at impact energies in the range 40-500 eV.

Absolute total cross section (TCS) measurements for electron scattering from 1-propanol molecules are reported for impact energies from 40 to 500 eV. These measurements were obtained using a new apparatus developed at Juiz de Fora Federal University-Brazil, which is based on the measurement of the attenuation of a collimated electron beam through a gas cell containing the molecules to be studied at a given pressure. Besides these experimental measurements, we have also calculated TCS using the Independent-Atom Model with Screening Corrected Additivity Rule and Interference (IAM-SCAR+I) approach with the level of agreement between them being typically found to be very good.

Total cross section of furfural by electron impact: Experiment and theory.

We present experimental total cross sections for electron scattering from furfural in the energy range from 10 to 1000 eV, as measured using a double electrostatic analyzer gas cell electron transmission experiment. These results are compared to theoretical data for furfural, as well as to experimental and theoretical values for the structurally similar molecules furan and tetrahydrofuran. The measured total cross section is in agreement with the theoretical results obtained by means of the independent-atom model with screening corrected additivity rule including interference method. In the region of higher electron energies, from 500 eV to 10 keV, the total electron scattering cross section is also estimated using a semi-empirical model based on the number of electrons and dipole polarizabilities of the molecular targets. Together with the recently measured differential and integral cross sections, and the furfural energy-loss spectra, the present total cross section data nearly complete the data set that is required for numerical simulation of low-energy electron processes in furfural, covering the range of projectile energies from a few electron volts up to 10 keV.

Elastic scattering and vibrational excitation for electron impact on para-benzoquinone.

We report on theoretical elastic and experimental vibrational-excitation differential cross sections (DCSs) for electron scattering from para-benzoquinone (C6H4O2), in the intermediate energy range 15-50 eV. The calculations were conducted with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that also now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (Nopen) at the static-exchange-plus-polarisation (Nopench-SEP) level was used to calculate the scattering amplitudes using a channel coupling scheme that ranges from 1ch-SE up to the 89ch-SEP level of approximation. We found that in going from the 38ch-SEP to the 89ch-SEP, at all energies considered here, the elastic DCSs did not change significantly in terms of both their shapes and magnitudes. This is a good indication that our SMCPP 89ch-SEP elastic DCSs are converged with respect to the multichannel coupling effect for the investigated intermediate energies. While agreement between our IAM-SCAR+I and SMCPP 89ch-SEP computations improves as the incident electron energy increases from 15 eV, overall the level of accord is only marginal. This is particularly true at middle scattering angles, suggesting that our SCAR and interference corrections are failing somewhat for this molecule below 50 eV. We also report experimental DCS results, using a crossed-beam apparatus, for excitation of some of the unresolved ("hybrid") vibrational quanta (bands I-III) of para-benzoquinone. Those data were derived from electron energy loss spectra that were measured over a scattered electron angular range of 10°-90° and put on an absolute scale using our elastic SMCPP 89ch-SEP DCS results. The energy resolution of our measurements was ∼80 meV, which is why, at least in part, the observed vibrational features were only partially resolved. To the best of our knowledge, there are no other experimental or theoretical vibrational excitation results against which we might compare the present measurements.

Electron impact ionization dynamics of para-benzoquinone.

Triple differential cross sections (TDCSs) for the electron impact ionization of the unresolved combination of the 4 highest occupied molecular orbitals (4b3g, 5b2u, 1b1g, and 2b3u) of para-benzoquinone are reported. These were obtained in an asymmetric coplanar geometry with the scattered electron being observed at the angles -7.5°, -10.0°, -12.5° and -15.0°. The experimental cross sections are compared to theoretical calculations performed at the molecular 3-body distorted wave level, with a marginal level of agreement between them being found. The character of the ionized orbitals, through calculated momentum profiles, provides some qualitative interpretation for the measured angular distributions of the TDCS.

Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods.

We present the experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectra of phenol covering for the first time the full 4.3-10.8 eV energy-range, with absolute cross sections determined. Theoretical calculations on the vertical excitation energies and oscillator strengths were performed using time-dependent density functional theory and the equation-of-motion coupled cluster method restricted to single and double excitations level. These have been used in the assignment of valence and Rydberg transitions of the phenol molecule. The VUV spectrum reveals several new features not previously reported in the literature, with particular reference to the 6.401 eV transition, which is here assigned to the 3sσ/σ(∗)(OH)←3π(3a″) transition. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of phenol in the earth's atmosphere (0-50 km).