Electron attachment to gas-phase uracil

We present results about dissociative electron attachment (DEA) to gas-phase uracil (U) for incident electron energies between 0 and 14 eV using a crossed electron/molecule beam apparatus. The most abundant negative ion formed via DEA is (U-H)-, where the resonance with the highest intensity appears at 1.01 eV. The anion yield of (U-H)- shows a number of peaks, which can be explained in part as being due to the formation of different (U-H)- isomers. Our results are compared with high level ab initio calculations using the G2MP2 method. There was no measurable amount of a parent ion U-. We also report the occurrence of 12 other fragments produced by dissociative electron attachment to uracil but with lower cross sections than (U-H)-. In addition we observed a parasitic contaminating process for conditions where uracil was introduced simultaneously with calibrant gases SF6 and CCl4 that leads to a sharp peak in the (U-H)- cross section close to 0 eV. For (U-H)- and all other fragments we determined rough measures for the absolute partial cross section yielding in the case of (U-H)- a peak value of sigma (at 1.01 eV)=3 x 10(-20) m2.     

Differential, partial and total electron impact ionization cross sections for SF(6)

Single and double differential ionization cross sections for the production of ions resulting from dissociative, single and double ionization of SF(6) by electron impact have been calculated using a semiempirical formulation based on the Jain-Khare approach. In addition, triple differential cross sections have been obtained for some of the doubly charged fragment ions at an incident electron energy of 100, 150, and 200 eV, respectively, and a fixed scattering angle of 30 degrees. As no previous data seem to exist for differential cross sections we have derived from these differential cross sections corresponding partial and total ionization cross sections from threshold up to 900 eV and compared those with the available theoretical and experimental data.     

Electron-impact ionization of CCl4 and CCl2F2

Absolute partial and total cross sections for electron-impact ionization of CCl4 and CCl2F2 are reported for electron energies from threshold to 1000 eV. The product ions are mass analyzed using a time-of-flight mass spectrometer and detected with a position-sensitive detector whose output demonstrates that all product ion species are collected with equal efficiency irrespective of their initial kinetic energies. Data are presented for production of CCl3(+), CCl2(+), CCl+, C+, Cl2(+), and CCl3(2+) from CCl4; and for production of CCl(2)F+, CClF2(+), CClF(+), (CCl+ + CF2(+)), Cl+, CF+, F+, and C+ from CCl2F2. Data are also reported for formation of (CCl2(+),Cl+) and (CCl+, Cl+) ion pairs from CCl4. The total cross section for each target is obtained as the sum of the partial cross sections. The overall uncertainty in the absolute cross sections for most of the singly charged ions is +/- 5-7 %. The present partial cross sections for lighter fragment ions are found to be considerably greater than had been previously reported but the most recent total cross section measurements agree well with those reported here. Neither the binary-encounter-Bethe theory nor the Deutsch-Mark theory reproduces the experimental cross sections correctly for both targets.     

The dependence of low-energy electron attachment to CF3Br on electron and vibrational energy

In a joint experimental and theoretical effort, we have studied dissociative electron attachment (DEA) to the CF3Br molecule at electron energies below 2 eV. Using two variants of the laser photoelectron attachment method with a thermal gas target (T(G) = 300 K), we measured the energy dependent yield for Br- formation over the range E = 3-1200 meV with resolutions of about 3 meV (E < 200 meV) and 35 meV. At the onsets for excitation of one and two quanta for the C-Br stretching mode nu3, downward cusps are detected. With reference to the recommended thermal (300 K) attachment rate coefficient k(A)(CF3Br) = 1.4 x 10(-8) cm3 s(-1), absolute cross sections have been determined for Br- formation. In addition, we studied Br- and (CF3Br)Br- formations with a seeded supersonic target beam (10% CF3Br in helium carrier gas, with a stagnation pressure of 1-4 bars and nozzle temperatures of 300 and 600 K) and found prominent structure in the anion yields due to cluster formation. Using the microwave pulse radiolysis swarm technique, allowing for controlled variation of the electron temperature by microwave heating, we studied the dependence of the absolute DEA rate coefficient on the mean electron energy E over the range of 0.04-2 eV at gas temperatures T(G) ranging from 173 to 600 K. For comparison with the experimental results, semiempirical resonance R-matrix calculations have been carried out. The input for the theory includes the known energetic and structural parameters of the neutral molecule and its anion; the parameters of the resonant anion curves are chosen with reference to the known thermal rate coefficient for the DEA process. For the gas temperature T(G) = 300 K, good overall agreement of the theoretical DEA cross section with the experimental results is observed; moreover, rate coefficients for Br- formation due to Rydberg electron transfer, calculated with both the experimental and the theoretical DEA cross sections, are found to agree with the previously reported absolute experimental values. At T(G) = 300 K, satisfactory agreement is also found between the calculated and experimental attachment rate coefficients for mean electron energies E = 0.04-2 eV. The strong increase of the measured rate coefficients with rising gas temperature, however, could be only partially recovered by the R-matrix results. The differences may result from the influence of thermal excitations of other vibrational modes not included in the theory.     

Vacuum-UV negative photoion spectroscopy of SF5CF3

Ion pair formation, generically described as AB-->A(+)+B(-), from vacuum-UV photoexcitation of trifluoromethyl sulfur pentafluoride, SF(5)CF(3), has been studied by anion mass spectrometry using synchrotron radiation in the photon energy range of 10-35 eV. The anions F(-), F(2)(-), and SF(x)(-) (x=1-5) are observed. With the exception of SF(5)(-), the anions observed show a linear dependence of signal with pressure, showing that they arise from ion pair formation. SF(5)(-) arises from dissociative electron attachment, following photoionization of SF(5)CF(3) as the source of low-energy electrons. Cross sections for anion production are put on to an absolute scale by calibration of the signal strengths with those of F(-) from both SF(6) and CF(4). Quantum yields for anion production from SF(5)CF(3), spanning the range of 10(-7)-10(-4), are obtained using vacuum-UV absorption cross sections. Unlike SF(6) and CF(4), the quantum yield for F(-) production from SF(5)CF(3) increases above the onset of photoionization.     

State-to-state differential and relative integral cross sections for rotationally inelastic scattering of H2O by hydrogen

State-to-state differential cross sections (DCSs) for rotationally inelastic scattering of H(2)O by H(2) have been measured at 71.2 meV (574 cm(-1)) and 44.8 meV (361 cm(-1)) collision energy using crossed molecular beams combined with velocity map imaging. A molecular beam containing variable compositions of the (J = 0, 1, 2) rotational states of hydrogen collides with a molecular beam of argon seeded with water vapor that is cooled by supersonic expansion to its lowest para or ortho rotational levels (J(KaKc) = 0(00) and 1(01), respectively). Angular speed distributions of fully specified rotationally excited final states are obtained using velocity map imaging. Relative integral cross sections are obtained by integrating the DCSs taken with the same experimental conditions. Experimental state-specific DCSs are compared with predictions from fully quantum scattering calculations on the most complete H(2)O-H(2) potential energy surface. Comparison of relative total cross sections and state-specific DCSs show excellent agreement with theory in almost all details.     

Low-energy electron attachment to SF6. II. Temperature and pressure dependences of dissociative attachment

Low-energy electron-molecule collisions, leading to dissociative attachment through metastable anionic states, are kinetically modeled within the framework of statistical unimolecular rate theory. The reaction e(-)+SF(6)-->SF(5)(-)+F is used as an illustrative example. The modeling is applied to new measurements of branching fractions for SF(5)(-) formation in the bath gas He between 360 and 670 K at 1 and 2 Torr, and between 490 and 620 K over the range of 0.3-9 Torr. The analysis of the data follows the previous kinetic modeling of the nondissociative electron attachment, e(-)+SF(6)-->SF(6)(-), from Part I of this series. Experimental results from the present work and the literature on branching fractions and total cross sections for anion formation as functions of electron energies, bath gas temperatures and pressures, as well as observation times are analyzed. The assumption of a participation of the electronic ground state of SF(6)(-) alone suffices to model the available experimental data. A value of the dissociation energy of SF(6)(-) into SF(5)(-)+F of E(0,dis)=1.61(+/-0.05) eV is determined, which may be compared to the electron affinity of SF(6), EA=1.20(+/-0.05) eV, such as derived in Part III of this series.     

Fragmentation of metastable SF(6)(-*) ions with microsecond lifetimes in competition with autodetachment

Fragmentation of metastable SF(6)(-*) ions formed in low energy electron attachment to SF(6) has been investigated. The dissociation reaction SF(6)(-*)-->SF(5) (-)+F has been observed approximately 1.5-3.4 micros and approximately 17-32 micros after electron attachment in a time-of-flight and a double focusing two sector field mass spectrometer, respectively. Metastable dissociation is observed with maximum intensity at approximately 0.3 eV between the SF(6)(-*) peak at zero and the SF(5)(-) peak at approximately 0.4 eV. The kinetic energy released in dissociation is low, with a most probable value of 18 meV. The lifetime of SF(6)(-*) decreases as the electron energy increases, but it is not possible to fit this decrease with statistical Rice-Ramsperger-Kassel/quasiequilibrium theory. Metastable dissociation of SF(6)(-*) appears to compete with autodetachment of the electron at all electron energies.     

Differential elastic electron scattering cross sections for CCl4 by 1.5-100 eV energy electron impact

We report absolute elastic differential, integral and momentum transfer cross sections for electron interactions with CCl(4). The incident electron energy range is 1.5-100 eV, and the scattered electron angular range for the differential measurements varies from 15°-130°. The absolute scale of the differential cross section was set using the relative flow technique with helium as the reference species. Comparison with previous total cross sections shows good agreement. Atomic-like behaviour in this scattering system is shown here for the first time, and is further investigated by comparing the CCl(4) elastic cross sections to recent results on the halomethanes and atomic chlorine at higher impact energies [H. Kato, T. Asahina, H. Masui, M. Hoshino, H. Tanaka, H. Cho, O. Ingólfsson, F. Blanco, G. Garcia, S. J. Buckman, and M. J. Brunger, J. Chem. Phys. 132, 074309 (2010)].     

Kinetics following addition of sulfur fluorides to a weakly ionized plasma from 300 to 500 K: rate constants and product determinations for ion-ion mutual neutralization and thermal electron attachment to SF5, SF3, and SF2

Rate constants for several processes including electron attachment to SF(2), SF(3), and SF(5) and individual product channels of ion-ion mutual neutralization between SF(6)(-), SF(5)(-), and SF(4)(-) with Ar(+) were determined by variable electron and neutral density attachment mass spectrometry. The experiments were conducted with a series of related neutral precursors (SF(6), SF(4), SF(5)Cl, SF(5)C(6)H(5), and SF(3)C(6)F(5)) over a temperature range of 300-500 K. Mutual neutralization rate constants for SF(6)(-), SF(5)(-), and SF(4)(-) with Ar(+) are reported with uncertainties of 10-25% and show temperature dependencies in agreement with the theoretical value of T(-0.5). Product branching in the mutual neutralizations is temperature independent and dependent on the electron binding energy of the anion. A larger fraction of product neutrals from the SF(6)(-) mutual neutralization (0.9 ± 0.1) are dissociated than in the SF(5)(-) mutual neutralization (0.65 ± 0.2), with the SF(4)(-) (0.7 ± 0.3) likely lying in between. Electron attachment to SF(5) (k = 2.0 × 10(-8) ±(1)(2) cm(3) s(-1) at 300 K) and SF(3) (4 ± 3 × 10(-9) cm(3) s(-1) at 300 K) show little temperature dependence. Rate constants of electron attachment to closed-shell SF(n) species decrease as the complexity of the neutral decreases.     

Virtual state scattering with cold electrons: para-xylene and para-difluorobenzene

The scattering of electrons with kinetic energies down to a few meV by para-xylene and para-difluorobenzene has been observed experimentally with an electron beam energy resolution of 0.95 to 1.5 meV (full width half maximum). At low electron energies the collisions can be considered as cold scattering events because the de Broglie wavelength of the electron is considerably larger than the target dimensions. The scattering cross sections measured rise rapidly at low energy due to virtual state scattering. The nature of this scattering process is discussed using s- and p-wave phase shifts derived from the experimental data. Scattering lengths are derived of, respectively, -9.5+/-0.5 and -8.0+/-0.5 a.u. for para-xylene and para-difluorobenzene. The virtual state effect is interpreted in terms of nuclear diabatic and partially adiabatic models, involving the electronic and vibronic symmetries of the unoccupied orbitals in the target species. The concept of direct and indirect virtual state scattering is introduced, through which the present species, in common with carbon dioxide and benzene, scatter through an indirect virtual state process, whereas other species, such as perfluorobenzene, scatter through a direct process.     

Elastic cross sections for electron scattering from GeF4: predominance of atomic-F in the high-energy collision dynamics

We report absolute differential cross sections (DCSs) for elastic electron scattering from GeF(4). The incident electron energy range was 3-200 eV, while the scattered electron angular range was typically 15°-150°. In addition, corresponding independent atom model (IAM) calculations, within the screened additivity rule (SCAR) formulation, were also performed. Those results, particularly for electron energies above about 10 eV, were found to be in good quantitative agreement with the present experimental data. Furthermore, we compare our GeF(4) elastic DCSs to similar data for scattering from CF(4) and SiF(4). All these three species possess T(d) symmetry, and at each specific energy considered above about 50 eV their DCSs are observed to be almost identical. These indistinguishable features suggest that high-energy elastic scattering from these targets is virtually dominated by the atomic-F species of the molecules. Finally, estimates for the measured GeF(4) elastic integral cross sections are derived and compared to our IAM-SCAR computations and with independent total cross section values.     

Electron scattering by methanol and ethanol: a joint theoretical-experimental investigation

We present a joint theoretical-experimental study on electron scattering by methanol (CH(3)OH) and ethanol (C(2)H(5)OH) in a wide energy range. Experimental differential, integral and momentum-transfer cross sections for elastic electron scattering by ethanol are reported in the 100-1000 eV energy range. The experimental angular distributions of the energy-selected electrons are measured and converted to absolute cross sections using the relative flow technique. Moreover, elastic, total, and total absorption cross sections for both alcohols are calculated in the 1-500 eV energy range. A complex optical potential is used to represent the dynamics of the electron-alcohol interaction, whereas the scattering equations are solved iteratively using the Pade?'s approximant technique. Our calculated data agree well with those obtained using the Schwinger multichannel method at energies up to 20 eV. Discrepancies at high energies indicate the importance of absorption effects, included in our calculations. In general, the comparison between our theoretical and experimental results, as well as with other experimental data available in the literature, also show good agreement. Nevertheless, the discrepancy between the theoretical and experimental total cross sections at low incident energies suggests that the experimental cross sections measured using the transmission technique for polar targets should be reviewed.     

Electron scattering from perfluorocyclobutane (c-C4F8)

We report experimental results for electron scattering from perfluorocyclobutane, c-C(4)F(8), obtained from measurements in our two laboratories. A set of differential, integral, and momentum transfer cross sections is provided for elastic scattering for incident electron energies from 1.5 to 100 eV. Inelastic scattering (vibrational excitation) cross sections have been measured for incident electron energies of 1.5, 2, 5, 6, and 7 eV. In order to investigate the role of intermediate negative ions (resonances) in the scattering process we have also measured an excitation function for elastic scattering and vibrational excitation of the ground electronic state of C(4)F(8) for incident energies between 0.6 and 20 eV. These results are compared with the limited amount of data available in the literature for scattering from this molecule.     

Low-energy electron collisions with glycine

We report cross sections for elastic electron scattering by gas phase glycine (neutral form), obtained with the Schwinger multichannel method. The present results are the first obtained with a new implementation that combines parallelization with OpenMP directives and pseudopotentials. The position of the well known π* shape resonance ranged from 2.3 eV to 2.8 eV depending on the polarization model and conformer. For the most stable isomer, the present result (2.4 eV) is in fair agreement with electron transmission spectroscopy assignments (1.93 ± 0.05 eV) and available calculations. Our results also point out a shape resonance around 9.5 eV in the A' symmetry that would be weakly coupled to vibrations of the hydroxyl group. Since electron attachment to a broad and lower lying σ* orbital located on the OH bond has been suggested the underlying mechanism leading to dissociative electron attachment at low energies, we sought for a shape resonance around ~4 eV. Though we obtained cross sections with the target molecule at the equilibrium geometry and with stretched OH bond lengths, least-squares fits to the calculated eigenphase sums did not point out signatures of this anion state (though, in principle, it could be hidden in the large background). The low energy (~1 eV) integral cross section strongly scales as the bond length is stretched, and this could indicate a virtual state pole, since dipole supported bound states are not expected at the geometries addressed here.     

Near-threshold electron attachment as Regge resonances: cross sections for K, Rb, and Cs atoms

We investigate the near-threshold formation of negative ions as Regge resonances in electron-atom scattering, with specific results obtained for e--K, e--Rb, and e--Cs. The complex angular momentum method, implemented within the Mulholland formulation of the total elastic cross sections, is employed. We demonstrate that for e--K, e--Rb, and e--Cs scattering, the near-threshold electron attachment cross sections are characterized by the Wigner threshold behavior, Ramsauer-Townsend minima, and Regge resonances, all discernible only through Regge partial cross section scrutiny. Regge partial, differential, and total elastic cross sections are presented and contrasted, as well as the differential cross section critical minima.     

Vibrational properties of disordered mono- and bilayers of physisorbed sulfur hexafluoride on Au(111)

We have examined the low-energy single-phonon vibrations of disordered mono- and bilayers of sulfur hexafluoride physisorbed on Au(111) with inelastic helium atom scattering. At monolayer coverages, SF6 exhibits a dispersionless Einstein mode at 3.6 +/- 0.4 meV. We observed two distinct overtones of this vibration as both creation and annihilation events at 7.1 +/- 0.7 meV and 10.9 +/- 1.4 meV, respectively. The overtones are harmonic multiples of the fundamental Einstein oscillation. Bilayers of SF6 exhibit a softer fundamental vibration with an excitation energy of 3.3 +/- 0.3 meV. This softening, due to the weaker SF6 binding, also results in reduced overtone energies of 6.6 +/- 0.7 meV and 9.8 +/- 0.6 meV. The disordered bilayer does not exhibit dispersion, indicating that the molecules are still behaving like Einstein oscillators and not beginning to act as bulk crystalline SF6. The results have improved our understanding of the adsorbate-substrate and interadsorbate interactions which govern the properties of this model molecular physisorption system.     

Measurements of differential cross sections fore-Ar,Kr, Xe scattering atE = 0.05 − 2 eV

Differential scattering experiments have been performed for the systemse-Ar, Kr, Xe in the energy rangeE=0.05 ? 2 eV and the angular range ?=20–100° using a crossed-beam arrangement. The measurements cover the region of the Ramsauer-Townsend minimum (for the first time in differential scattering using modern techniques) and show the drastic variation of the cross section over this energy range. For these experiments, a new electron spectrometer has been developed which is especially designed to allow measurements at very low collision energies under well controlled conditions. In the present work, the measurements could be extended down to 50 meV. The energy resolution was ΔE = 10 meV (FWHM). Absolute cross sections and the correct transmission properties of the systems are determined usinge-He scattering as a reference system. The experimental data are analysed by the MERT method which allows to extrapolate the cross sections to zero energy. On the basis of the MERT parameters, detailed comparison is made with other work.     

Total cross sections for electron scattering by polyatomic molecules at 10–1000 eV: C2H2, C2H4, C2H6, C3H6, C3H8 and C4H8

A model complex optical potential (composed of static, exchange, polarization and absorption terms) is employed to calculate the total (elastic and inelastic) electron-atom scattering cross sections from the corresponding atomic wave function at the Hartree-Fock level. The total cross sections (TCS) for electron scattering by their corresponding molecules (C₂H₂, C₂H₄, C₂H₆, C₃H₆, C₃H₈ and C₄H₈) are firstly obtained by the use of the additivity rule over an incident energy range of 10–1000 eV. The qualitative molecular results are compared with experimental data and other calculations wherever available, good agreement is obtained in intermediate-and high-energy region.     

Scattering of N(2)O on electron impact over an extensive energy range (0.1 eV-2000 eV)

We report electron impact total cross sections, Q(T), for e-N(2)O scattering over an extensive range of impact energies approximately from 0.1 eV to 2000 eV. We employ an ab initio calculation using R-matrix formalism below the ionization threshold of the target and above it we use the well established spherical complex optical potential to compute the cross sections. Total cross section is obtained as a sum of total elastic and total electronic excitation cross sections below the ionization threshold and above the ionization threshold as a sum of total elastic and total inelastic cross sections. Ample cross section data for e-N(2)O scattering are available at low impact energies and hence meaningful comparisons are made. Good agreement is observed with the available theoretical as well as experimental results over the entire energy range studied here.