Recent advances in the application of the Schwinger multichannel method with pseudopotentials to electron-molecule collisions

The Schwinger multichannel method [K. Takatsuka and V. McKoy, Phys. Rev. A 30, 1734 (1984)], which is based on the Schwinger variational principle for the scattering amplitude [J. Schwinger, Phys. Rev. 72, 742 (1947)], was designed to account for exchange, polarization and electronically multichannel coupling effects in the low-energy region of electron scattering from molecules with arbitrary geometry. The applications of the method became more ambitious with the availability of computer power combined with parallel processing, use of norm-conserving pseudopotentials and improvement of the description of target excited states (minimal orbital basis for single configuration interaction). The most recent applications involving 33 and 45 electronically open channels for phenol and ethylene molecules, represent good examples of the present status of the method. In this colloquium, we review the strategy and point out new directions to apply the method in its full extension

The electron-furfural scattering dynamics for 63 energetically open electronic states

We report on integral-, momentum transfer-and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C5H4O2). The calculations were performed 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 now incorporates a further interference (I) term. The SMCPP 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 at impact energies lying between 5 eV and 50 eV, using a channel coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections. (C) 2016 AIP Publishing LLC

Low energy elastic and electronically inelastic electron scattering from biomolecules.

Reactions initiated by collisions with low-energy secondary electrons has been found to be the prominent\ud mechanism toward the radiation damage on living tissues through DNA strand breaks. Now it is widely accepted\ud that during the interaction with these secondary species the selective breaking of chemical bonds is triggered\ud by dissociative electron attachment (DEA), that is, the capture of the incident electron and the formation\ud of temporary negative ion states [1,2,3]. One of the approaches largely used toward a deeper understanding\ud of the radiation damage to DNA is through modeling of DEA with its basic constituents (nucleotide bases,\ud sugar and other subunits). We have tried to simplify this approach and attempt to make it comprehensible\ud at a more fundamental level by looking at even simple molecules. Studies involving organic systems such as\ud carboxylic acids, alcohols and simple ¯ve-membered heterocyclic compounds are taken as starting points for\ud these understanding. In the present study we investigate the role played by elastic scattering and electronic\ud excitation of molecules on electron-driven chemical processes. Special attention is focused on the analysis of\ud the in°uence of polarization and multichannel coupling e®ects on the magnitude of elastic and electronically\ud inelastic cross-sections. Our aim is also to investigate the existence of resonances in the elastic and electronically\ud inelastic channels as well as to characterize them with respect to its type (shape, core-excited or Feshbach),\ud symmetry and position. The relevance of these issues is evaluated within the context of possible applications\ud for the modeling of discharge environments and implications in the understanding of mutagenic rupture of DNA\ud chains. The scattering calculations were carried out with the Schwinger multichannel method (SMC) [4] and\ud its implementation with pseudopotentials (SMCPP) [5] at di®erent levels of approximation for impact energies\ud ranging from 0.5 eV to 30 eV.\ud References\ud [1] B. Boudai®a, P. Cloutier, D. Hunting, M. A. Huels and L. Sanche, Science 287, 1658 (2000). [2] X. Pan, P.\ud Cloutier, D. Hunting and L. Sanche, Phys. Rev. Lett. 90, 208102 (2003). [3] F. Martin, P. D. Burrow, Z. Cai,\ud P. Cloutier, D. Hunting and L. Sanche, Phys. Rev. Lett. 93, 068101 (2004). [4] K. Takatsuka and V. McKoy,\ud Phys. Rev. A 24, 2437 (1981); ibid. Phys. Rev. A 30, 1734 (1984). [5] M. H. F. Bettega, L. G. Ferreira and\ud M. A. P. Lima, Phys. Rev. A 47, 1111 (1993)

Integral elastic, electronic-state, ionization, and total cross sections for electron scattering with furfural

We report absolute experimental integral cross sections (ICSs) for electron impact excitation of bands of electronic-states in furfural, for incident electron energies in the range 20-250 eV. Wherever possible, those results are compared to corresponding excitation cross sections in the structurally similar species furan, as previously reported by da Costa et al. [Phys. Rev. A 85, 062706 (2012)] and Regeta and Allan [Phys. Rev. A 91, 012707 (2015)]. Generally, very good agreement is found. In addition, ICSs calculated with 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 for electron-furfural scattering. Where possible, those calculated IAM-SCAR+I ICS results are compared against corresponding results from the present measurements with an acceptable level of accord being obtained. Similarly, but only for the band I and band II excited electronic states, we also present results from our Schwinger multichannel method with pseudopotentials calculations. Those results are found to be in good qualitative accord with the present experimental ICSs. Finally, with a view to assembling a complete cross section data base for furfural, some binary-encounter-Bethe-level total ionization cross sections for this collision system are presented. (C) 2016 AIP Publishing LLC

Elastic scattering of low-energy electrons by BF

We present integral, differential and momentum transfer cross sections for elastic scattering of low-energy electrons by boron trifluoride molecules. The cross sections were obtained with the Schwinger multichannel method implemented with pseudopotentials. The calculations were performed in the static-exchange and in the static-exchange-polarization approximations for energies from 0.1 to 10 eV. Our results indicate that BF3 has a shape resonance in the B2 symmetry located at around 3.5 eV, in agreement with the experimental measurements of 3.8 eV, 3.54 eV and of 3.6 eV reported by [M. Tronc et al., J. Phys. B 15, L253 (1982)], by [J.A. Tossell et al., Int. J. Quantum Chem. 29, 1117 (1986)] and by [C. Szmytkowski et al., J. Chem. Phys. 121, 1790 (2004)] respectively. We also report a Ramsauer-Townsend minimum at around 0.7 eV, in conformity with the observations of [S.R. Hunter et al., J. Appl. Phys. 65, 1858 (1989); Z. Nikitović et al., Acta Phys. Polon. A 117, 748 (2010)], and [P.X. Hien et al., J. Phys. Soc. Jpn 82, 034301 (2013)]. Our elastic integral cross section is compared with calculated elastic cross sections of [J.A. Tossell et al., Int. J. Quantum Chem. 29, 1117 (1986)] and of [M. Radmilović-Radjenović et al., Publ. Astron. Obs. Belgrade 84, 57 (2008)] and with the experimental total cross section data of [C. Szmytkowski et al., J. Chem. Phys. 121, 1790 (2004)]. Although all these studies reported the presence of the shape resonance, there are some discrepancies in the magnitude and shape among the cross sections

Electronic excitation of benzene by low energy electron impact and the role of higher lying Rydberg states

Benzene is undoubtedly one of the most studied target molecules in electron scattering experiments and calculations. However, there is still a huge knowledge gap on the electronic excitation cross sections of this fundamental collision. Here, we report calculated differential and integral cross sections for elastic and electronic excitation, as well as total cross sections, for electron scattering by the benzene molecule, for impact energies in the 10–50 eV range. We have employed the Schwinger multichannel method, in two levels of approximation. By including extra diffuse functions in the second calculation, the role of higher lying Rydberg states in the multichannel coupling scheme was assessed. We found that such states have minor effects on the elastic and total cross sections. In contrast, the electronic excitation cross sections of the lower-lying bands decrease in magnitude when accounting for the higher Rydberg states, and this effect becomes more pronounced at lower impact energies. Our computed elastic cross sections are in quite good agreement with the available experimental data, whereas the comparison for the electronic excitation channels is still satisfactory. We also discuss the need for accurate excitation energies in order to properly compare theoretical and experimental electronic excitation cross sections

Electron scattering by biomass molecular fragments: useful data for plasma applications?

CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORRecent data obtained for electron scattering by biomass molecular fragments, indicated that low-energy resonances may have an important role in the de-lignification of biomass through a plasma pretreatment. To support these findings, we present new experimental evidence of the predicted dissociation pathways on plasma treatment of biomass. An important question is how accurate must the experimental and/or the theoretical data be in order to indicate that plasma modelings can be really useful in understanding plasma applications? In this paper, we initiate a discussion on the role of data accuracy of experimental and theoretical electron-molecule scattering cross sections in plasma modeling. First we review technological motivations for carrying out electron-molecule scattering studies. Then we point out the theoretical and experimental limitations that prevent us from obtaining more accurate cross sections. We present a few examples involving biomass molecular fragments, to illustrate theoretical inaccuracies on: resonances positions and widths, electronic excitation, superelastic cross sections from metastable states and due to multichannel effects on the momentum transfer cross sections. On the experimental side we briefly describe challenges in making absolute cross sections measurements with biomass species and radicals. And finally, through a simulation of a N-2 plasma, we illustrate the impact on the simulation due to inaccuracies on the resonance positions and widths and due to multichannel effects on the momentum transfer cross sections.Recent data obtained for electron scattering by biomass molecular fragments, indicated that low-energy resonances may have an important role in the de-lignification of biomass through a plasma pretreatment. To support these findings, we present new experimental evidence of the predicted dissociation pathways on plasma treatment of biomass. An important question is how accurate must the experimental and/or the theoretical data be in order to indicate that plasma modelings can be really useful in understanding plasma applications? In this paper, we initiate a discussion on the role of data accuracy of experimental and theoretical electron-molecule scattering cross sections in plasma modeling. First we review technological motivations for carrying out electron-molecule scattering studies. Then we point out the theoretical and experimental limitations that prevent us from obtaining more accurate cross sections. We present a few examples involving biomass molecular fragments, to illustrate theoretical inaccuracies on: resonances positions and widths, electronic excitation, superelastic cross sections from metastable states and due to multichannel effects on the momentum transfer cross sections. On the experimental side we briefly describe challenges in making absolute cross sections measurements with biomass species and radicals. And finally, through a simulation of a N-2 plasma, we illustrate the impact on the simulation due to inaccuracies on the resonance positions and widths and due to multichannel effects on the momentum transfer cross sections.708112CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORSem informaçãoSem informação005-2014The authors acknowledge support from the Brazilian agency Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). R.F. da C., M.T. do N.V., J.A.F. and M.A.P.L. acknowledge support from Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP). M.A.R. acknowledges support from the Brazilian Agency Coordenação de Aperfeiçoamento de Pessoal de Nível Superior under the grant Capes/ITA 005-2014. M.J.B. acknowledges the Australian Research Council (ARC) for some financial support and also thanks CNPq for his Special Visiting Professor award at the Federal University of Juiz de Fora

Low-energy Electron Collisions With Pyrrole.

We report cross sections for low-energy elastic electron scattering by pyrrole, obtained with the Schwinger multichannel method implemented with pseudopotentials. Our calculations indicate pi( *) shape resonances in the B(1) and A(2) symmetries, and two sigma( *) resonances in the A(1) symmetry (the system belongs to the C(2v) point group). The present assignments of pi( *) resonances are very close to those previously reported for the isoelectronic furan molecule, in agreement with electron transmission spectra. The lowest-lying sigma( *) anion is localized on the N-H bond and provides a dissociation coordinate similar to those found in the hydroxyl groups of organic acids and alcohols. This sigma(NH) ( *) resonance overlaps the higher-lying pi( *) resonance (possibly both pi( *) states) and could give rise to direct and indirect dissociation pathways, which arise from electron attachment to sigma( *) and pi( *) orbitals, respectively. The photochemistry of pyrrole and 9-H adenine is similar, in particular with respect to the photostability mechanism that allows for the dissipation of the photon energy, and we believe pyrrole would also be a suitable prototype for studies of dissociative electron attachment (DEA) to DNA bases. We point out the connection between the mechanisms of photostability and DEA since both arise from the occupation of sigma( *) and pi( *) orbitals in neutral excited states and in anion states, respectively.13220430