Absolute Integral Cross Sections Research Articles

A new instrumentation for simultaneous terahertz and mid-infrared spectroscopy in corrosive gaseous mixtures.

The correct interpretation of infrared (IR) observations of planetary atmospheres requires an accurate knowledge of temperature and partial and global pressures. Precise laboratory measurements of absorption intensities and line profiles, in the 200-350K temperature range, are, therefore, critical. However, for gases only existing in complex chemical equilibria, such as nitrous or hypobromous acids, it is not possible to rely on absolute pressure measurements to measure absolute integrated optical absorption cross sections or IR line intensities. To overcome this difficulty, a novel dual-beam terahertz (THz)/mid-IR experimental setup has been developed, relying on the simultaneous use of two instruments. The setup involves a newly constructed temperature-controlled (200-350K) cross-shaped absorption cell made of inert materials. The cell is traversed by the mid-IR beam from a high-resolution Fourier transform spectrometer using along a White-cell optical configuration providing absorption path lengths from 2.8 to 42m and by a THz radiation beam (82.5GHz to 1.1THz), probing simultaneously the same gaseous sample. The THz channel records pure rotational lines of molecules for which the dipole moment was previously measured with high precision using Stark spectroscopy. This allows for a determination of the partial pressure in the gaseous mixture and enables absolute line intensities to be retrieved for the mid-IR range. This new instrument opens a new possibility for the retrieval of spectroscopic parameters for unstable molecules of atmospheric interest. The design and performance of the equipment are presented and illustrated by an example of simultaneous THz and mid-IR measurement on nitrous acid (HONO) equilibrium.

Quantum electronic control on chemical activation of methane by collision with spin-orbit state selected vanadium cation.

By coupling a newly developed quantum-electronic-state-selected supersonically cooled vanadium cation (V+) beam source with a double quadrupole-double octopole (DQDO) ion-molecule reaction apparatus, we have investigated detailed absolute integral cross sections (σ's) for the reactions, V+[a5DJ (J = 0, 2), a5FJ (J = 1, 2), and a3FJ (J = 2, 3)] + CH4, covering the center-of-mass collision energy range of Ecm = 0.1-10.0 eV. Three product channels, VH+ + CH3, VCH2+ + H2, and VCH3+ + H, are unambiguously identified based on Ecm-threshold measurements. No J-dependences for the σ curves (σ versus Ecm plots) of individual electronic states are discernible, which may indicate that the spin-orbit coupling is weak and has little effect on chemical reactivity. For all three product channels, the maximum σ values for the triplet a3FJ state [σ(a3FJ)] are found to be more than ten times larger than those for the quintet σ(a5DJ) and σ(a5FJ) states, showing that a reaction mechanism favoring the conservation of total electron spin. Without performing a detailed theoretical study, we have tentatively interpreted that a weak quintet-to-triplet spin crossing is operative for the activation reaction. The σ(a5D0, a5F1, and a3F2) measurements for the VH+, VCH2+, and VCH3+ product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH4 have allowed the determination of the 0 K bond dissociation energies: D0(V+-H) = 2.02 (0.05) eV, D0(V+-CH2) = 3.40 (0.07) eV, and D0(V+-CH3) = 2.07 (0.09) eV. Detailed branching ratios of product ion channels for the titled reaction have also been reported. Excellent simulations of the σ curves obtained previously for V+ generated by surface ionization at 1800-2200 K can be achieved by the linear combination of the σ(a5DJ, a5FJ, and a3FJ) curves weighted by the corresponding Boltzmann populations of the electronic states. In addition to serving as a strong validation of the thermal equilibrium assumption for the populations of the V+ electronic states in the hot filament ionization source, the agreement between these results also confirmed that the V+(a5DJ, a5FJ, and a3FJ) states prepared in this experiment are in single spin-orbit states with 100% purity.

Chemical Activation of Water Molecule by Collision with Spin–Orbit-State-Selected Vanadium Cation: Quantum-Electronic-State Control of Chemical Reactivity

We have obtained absolute integral cross sections (σ's) for the reactions of spin-orbit-state-selected vanadium cations, V+[a5DJ(J = 0, 2), a5FJ(J = 1, 2), and a3FJ(J = 2, 3)], with a water molecule (H2O) in the center-of-mass collision energy range Ecm = 0.1-10.0 eV. On the basis of these state-selected σ curves (σ versus Ecm plots) observed, three reaction product channels, VO+ + H2, VH+ + OH, and VOH+ + H, from the V+ + H2O reaction are unambiguously identified. Contrary to the previous guided ion beam study of the V+(a5DJ) + D2O reaction, we have observed the formation of the VO+ + H2 channel from the V+(a5DJ) + H2O ground reactant state at low Ecm's (<3.0 eV). No spin-orbit J-state dependences for the σ curves of individual electronic states are discernible, indicating that spin-orbit interactions are weak with little effect on chemical reactivity of the titled reaction. For the three product channels identified, the triplet σ(a3FJ) values are overwhelmingly higher than the quintet σ(a5DJ) and σ(a5FJ) values, showing that the reaction is governed by a "weak quintet-triplet spin crossing" mechanism, favoring the conservation of total electron spins. The σ curves for exothermic product channels are found to exhibit a rapid decreasing profile as Ecm is increased, an observation consistent with the prediction of the charge-dipole and induced-dipole orbiting model. This experiment shows that the V+ + H2O reaction can be controlled effectively to produce predominantly the VO+ + H2 channel via the V+(a3FJ) + H2O reaction at low Ecm's (≤0.1 eV) and that the ion-molecule reaction dynamics can be altered readily by selecting the electronic state of V+ cation. On the basis of the measured Ecm thresholds for the σ(a5DJ, a5FJ, and a3FJ: VH+) and σ(a5DJ, a5FJ, and a3FJ: VOH+) curves, we have deduced upper bound values of 2.6 ± 0.2 and 4.3 ± 0.3 eV for the 0 K bond dissociation energies, D0(V+-H) and D0(V+-OH), respectively. After correcting for the kinetic energy distribution resulting from the Doppler broadening effect of the H2O molecule, we obtain D0(V+-H) = 2.2 ± 0.2 eV and D0(V+-OH) = 4.0 ± 0.3 eV, which are in agreement with D0 determinations obtained by σ curve simulations.

Chemical activation of oxygen molecule by quantum electronic state selected vanadium cation: observation of spin–orbit state effects

By employing two-colour laser pulsed field ionisation-photoion (PFI-PI) double-quadrupole-double-octopole ion-molecule apparatus, we have examined the absolute integral cross-section (σ) for the reaction between vanadium cation (V+) and oxygen molecule (O2), covering the centre-of-mass kinetic energy (E cm) range of 0.2–10.0 eV. Here, V+ ion was prepared exclusively in its lowest 13 spin–orbit or J-states, a5DJ=0-4, a5FJ=1-5 , and a3FJ=2-4. The formation of VO+ + O is identified as the only product channel for these exothermic reactions. At E cm = 0.2–5.0 eV, the σ values for the three electronic states are found to be in the order: σ(a3FJ) > σ(a5DJ) > σ(a5FJ), whereas these cross-sections become nearly identical at E cm = 5.0–10.0 eV. This observation has been rationalised by collision-mediated non-adiabatic electronic transitions. The J-state effect for the V+(a3F2, 3) + O2 reactions are unambiguously identified for the first time for a reaction involving a transition metal cation. This J-state dependent chemical reactivity observed calls for rigorous theoretical interpretation. The fact that chemical reactivity for the a5FJ excited state is lower than that for the a5DJ ground state indicates that the difference in chemical reactivity is originated from quantum-electronic-state instead of energy effects.

Experimental study of the proton-transfer reaction C + H2+ → CH+ + H and its isotopic variant (D2+).

We report absolute integral cross section (ICS) measurements using a dual-source merged-fast-beams apparatus to study the titular reactions over the relative translational energy range of Er ∼ 0.01-10 eV. We used photodetachment of C- to produce a pure beam of atomic C in the ground electronic 3P term, with statistically populated fine-structure levels. The H2+ and D2+ were formed in an electron impact ionization source, with well known vibrational and rotational distributions. The experimental work is complemented by a theoretical study of the CH2+ electronic system in the reactant and product channels, which helps to clarify the possible reaction mechanisms underlying the ICS measurements. Our measurements provide evidence that the reactions are barrierless and exoergic. They also indicate the apparent absence of an intermolecular isotope effect, to within the total experimental uncertainties. Capture models, taking into account either the charge-induced dipole interaction potential or the combined charge-quadrupole and charge-induced dipole interaction potentials, produce reaction cross sections that lie a factor of ∼4 above the experimental results. Based on our theoretical study, we hypothesize that the reaction is most likely to proceed adiabatically through the 14A' and 14A'' states of CH2+via the reaction C(3P) + H2+(2Σ+g) → CH+(3Π) + H(2S). We also hypothesize that at low collision energies only H2+(v ≤ 2) and D2+(v ≤ 3) contribute to the titular reactions, due to the onset of dissociative charge transfer for higher vibrational v levels. Incorporating these assumptions into the capture models brings them into better agreement with the experimental results. Still, for energies ⪅0.1 eV where capture models are most relevant, the modified charge-induced dipole model yields reaction cross sections with an incorrect energy dependence and lying ∼10% below the experimental results. The capture cross section obtained from the combined charge-quadrupole and charge-induced dipole model better matches the measured energy dependence but lies ∼30-50% above the experimental results. These findings provide important guidance for future quasiclassical trajectory and quantum mechanical treatments of this reaction.

Absolute Infrared Absorption Cross Section of the Simplest Criegee Intermediate Near 1285.7 cm-1.

The ν4 fundamental of the simplest Criegee intermediate, CH2OO, has been monitored with high-resolution infrared (IR) transient absorption spectroscopy under total pressures of 4-94 Torr. This IR spectrum provides an unambiguous identification of CH2OO and is potentially useful to determine the number density of CH2OO in various laboratory studies. Here we utilized an ultraviolet (UV) and IR coupled spectrometer to measure the UV and IR absorption spectra of CH2OO simultaneously; the absolute IR cross section can then be determined by using a known UV cross section. Due to significant pressure broadening in the studied pressure range, we integrated the IR absorption spectra between 1285.2 and 1286.4 cm-1 (covering the Q branch), and then we converted this integrated absorbance to the absolute integral IR cross section of CH2OO (for the Q branch); its absolute value is (3.7 ± 0.6) × 10-19 cm·molecule-1 or 2.2 ± 0.4 km·mol-1. The whole rotational band (P, Q, and R branches) can be adequately simulated by using the precise spectroscopic parameters from the literature, yielding the absolute integral IR cross section (full ν4 band) to be 19.2 ± 3.5 km·mol-1. For a practical detection of CH2OO, this work also reports the peak cross section as a function of total pressure (4-94 Torr O2). At low pressure (≤4 Torr), where the pressure broadening is insignificant, the absorption cross section of the highest peak is (6.2 ± 0.9) × 10-18 cm2·molecule-1 (at the system line width of 0.004 cm-1 fwhm).

Quantum-vibrational-state-selected Integral Cross Sections and Product Branching Ratios for the Ion-molecule Reactions of N2 +(X2Σg +; v+ = 0–2) + H2O and H2O+(X2B1: v1 +v2 +v3 + = 000 and 100) + N2 in the Collision Energy Range of 0.04–10.00 eV

Abstract By combining the vacuum ultraviolet laser pulsed field ionization-photoion (VUV-PFI-PI) ion source with the double quadruple-double octopole (DQDO) ion-guided mass spectrometer, we have investigated the center-of-mass collision energy (E cm) and vibrational-state dependences of the ion-molecule reactions of and and 100) + N2 covering the E cm range of 0.04–10.00 eV. The absolute integral cross sections (σ’s) for the charge transfer (CT) [σ CT(v +)] channel to form H2O+ and the H-atom transfer (HT) [σ HT(v +)] channel to form N2H+ from the reactions have been determined, revealing the dominance of σ CT(v +) over σ HT(v +) at E cm = 0.04–8.00 eV. The E cm dependence of σ CT(v +) at low E cm &lt; 1.00 eV is consistent with the long-range ion-dipole and ion-induced dipole CT mechanism. Minor vibrational inhibition is observed for the σ CT(v +) at low E cm ≤ 0.30 eV, which can be rationalized by the near-resonance CT mechanism. While the σ HT(v +) values are consistent with previous measurements, the σ CT(v +) obtained here resolve a hump at E cm = 1.0–5.0 eV, which is not observed previously. This feature is attributed to the formation of excited H2O+(B 2 B 2) ions via the collision-assisted CT mechanism. The branching ratio for product H2O+[BR(H2O+)] is found to be constant (0.82 ± 0.05) at E cm = 0.04–1.00 eV, and is independent of v + vibrational state. As E cm is increased from 1.0 eV, the BR(H2O+) reaches a maximum of 0.93 at E cm ≈ 3.00 eV, followed by the decline to 0.20 at E cm ≥ 9.0 eV, where σ HT(v +) becomes dominant compared to σ CT(v +). The ) for the formation of N2H+ via the proton transfer (PT) channel of the H2O+(X 2 B 1: 000 and 100) + N2 reaction has also been measured. The comparison of the σ PT(000 and 100) values reveals significant (100) vibrational enhancement. Furthermore, the E cm thresholds determined here for σ PT(000 and 100) are in agreement with their thermochemical thresholds. The BR and σ values determined here are valuable for modeling the ion chemistry occurring in planetary atmospheres, in addition to serving as benchmarks for state-of-the-art quantum dynamics calculations.

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.

Absolute cross section measurements for the scattering of low- and intermediate-energy electrons from PF3. II. Inelastic scattering of vibrational and electronic excitations.

As a sequel paper to our study of the elastic scattering for electron collisions with phosphorus trifluoride, PF3 molecules, we report absolute inelastic differential and integral cross sections (DCS and ICS) of vibrational excitations for the compound fundamental vibrational modes v13 (v1 + v3), v24 (v2 + v4), and their sum in the impact energy range of 2.0-10 eV and over a scattering angle range of 20°-130°. The measured angular distributions of scattered electron intensities for the present inelastic scattering are normalized to the elastic peak intensity corresponding to the DCSs of He. These vibrational excitation measurements demonstrate the presence of resonances around 2 eV and also around 6-10 eV. In addition, a generalized oscillator strength analysis is applied to derive oscillator strength f0-values and (unscaled Born) ICSs from the corresponding DCSs measured for the low-lying optically allowed 8a1-1 → 7e (σ*) excitation band, which is assigned as the Jahn-Teller splitting and 8a1-1 → 4s Rydberg transition at impact energies of 100, 200, and 300 eV, over a scattering angle range of 1.0°-15°. The f0-values obtained in the present study are compared with the results of previous photoabsorption and pseudo-optical measurements. The unscaled Born ICSs are compared with the binary-encounter f-scaled Born ICSs estimated over a wide impact energy region from the excitation thresholds.

A quantum-rovibrational-state-selected study of the reaction in the collision energy range of 0.05-10.00 eV: translational, rotational, and vibrational energy effects.

We report detailed absolute integral cross sections (σ's) for the quantum-rovibrational-state-selected ion-molecule reaction in the center-of-mass collision energy (Ecm) range of 0.05-10.00 eV, where (vvv) = (000), (100), and (020), and . Three product channels, HCO+ + OH, HOCO+ + H, and CO+ + H2O, are identified. The measured σ(HCO+) curve [σ(HCO+) versus Ecm plot] supports the hypothesis that the formation of the HCO+ + OH channel follows an exothermic pathway with no potential energy barriers. Although the HOCO+ + H channel is the most exothermic, the σ(HOCO+) is found to be significantly lower than the σ(HCO+). The σ(HOCO+) curve is bimodal, indicating two distinct mechanisms for the formation of HOCO+. The σ(HOCO+) is strongly inhibited at Ecm < 0.4 eV, but is enhanced at Ecm > 0.4 eV by (100) vibrational excitation. The Ecm onsets of σ(CO+) determined for the (000) and (100) vibrational states are in excellent agreement with the known thermochemical thresholds. This observation, along with the comparison of the σ(CO+) curves for the (100) and (000) states, shows that kinetic and vibrational energies are equally effective in promoting the CO+ channel. We have also performed high-level ab initio quantum calculations on the potential energy surface, intermediates, and transition state structures for the titled reaction. The calculations reveal potential barriers of ≈0.5-0.6 eV for the formation of HOCO+, and thus account for the low σ(HOCO+) and its bimodal profile observed. The Ecm enhancement for σ(HOCO+) at Ecm ≈ 0.5-5.0 eV can be attributed to the direct collision mechanism, whereas the formation of HOCO+ at low Ecm < 0.4 eV may involve a complex mechanism, which is mediated by the formation of a loosely sticking complex between HCO+ and OH. The direct collision and complex mechanisms proposed also allow the rationalization of the vibrational inhibition at low Ecm and the vibrational enhancement at high Ecm observed for the σ(HOCO+).

Excitation of the lowest electronic transitions in ethanol by low-energy electrons

We report absolute differential and integral cross sections for electronic excitation of ethanol, by low-energy electron impact. Cross sections for low-lying excited states were measured at incident electron energies from 9 to 20 eV and at scattering angles from through . Our results include cross sections for excitation of the and states as well as for the + and + cross section sums. Corresponding calculations were also performed using the Schwinger multichannel method, within an 11-channel close-coupling scheme.

ABSOLUTE INTEGRAL CROSS SECTIONS FOR THE STATE-SELECTED ION–MOLECULE REACTION ; v+ = 0–2) + C2H2 IN THE COLLISION ENERGY RANGE OF 0.03–10.00 eV

ABSTRACT Using the vacuum ultraviolet laser pulsed field ionization-photoion source, together with the double-quadrupole–double-octopole mass spectrometer developed in our laboratory, we have investigated the state-selected ion–molecule reaction ; v + = 0–2, N+ = 0–9) + C2H2, achieving high internal-state selectivity and high kinetic energy resolution for reactant ions. The charge transfer (CT) and hydrogen-atom transfer (HT) channels, which lead to the respective formation of product and N2H+ ions, are observed. The vibrationally selected absolute integral cross sections for the CT [σ CT(v +)] and HT [[σ HT(v +)] channels obtained in the center-of-mass collision energy (E cm) range of 0.03–10.00 eV reveal opposite E cm dependences. The σ CT(v +) is found to increase as E cm is decreased, and is consistent with the long-range exothermic CT mechanism, whereas the E cm enhancement observed for the σ HT(v +) suggests effective coupling of kinetic energy to internal energy, enhancing the formation of N2H+. The σ HT(v +) curve exhibits a step at E cm = 0.70–1.00 eV, suggesting the involvement of the excited state in the HT reaction. Contrary to the strong E cm dependences for σ CT(v +) and σ HT(v +), the effect of vibrational excitation of on both the CT and HT channels is marginal. The branching ratios and cross sections for the CT and HT channels determined in the present study are useful for modeling the atmospheric compositions of Saturn's largest moon, Titan. These cross sections and branching ratios are also valuable for benchmarking theoretical calculations on chemical dynamics of the titled reaction.

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.

Cross sections for electron collisions with H2O: elastic scattering and electronic excitation for the ã3B1 and Ã1B1 states

SynopsisWe report absolute differential cross sections (DCSs) and integral cross sections (ICSs) for the electronic excitation to the ã3B1 and Ã1B1 states as well as the elastic scattering of H2O molecules. The measurements are performed in the scattering angle range of 10 - 130o, and impact energies 15, 20, 30 eV for the electronic excitations and energy range 2.0 - 100 eV for the elastic scattering, respectively.

Electron collisions with ammonia and formamide in the low- and intermediate-energy ranges

We report an investigation on electron collisions with two nitrogen-containing compounds, namely ammonia (${\mathrm{NH}}_{3}$) and formamide (${\mathrm{NH}}_{2}\mathrm{CHO}$). For ammonia, both theoretical and experimental differential, integral, and momentum-transfer cross sections, as well as calculated grand-total and total absorption cross sections, are reported in the 50--500 eV incident energy range. Calculated results of various cross sections are also reported for energies below 50 eV. Experimentally, angular distributions of the scattered electrons were measured using a crossed electron beam-molecular beam geometry and then converted to absolute differential cross sections using the relative flow technique. Absolute integral and momentum-transfer cross sections for elastic ${e}^{\ensuremath{-}}$-ammonia scattering were also derived from the measured differential cross sections. For formamide, only theoretical cross sections are presented in the 1--500 eV incident energy range. A single-center-expansion technique combined with the method of Pad\'e was used in our calculations. For both targets, our calculated cross sections are compared with the present measured data and with the theoretical and experimental data available in the literature and show generally good agreement. Moreover, for formamide, two shape resonances located at 3.5 eV and 15 eV which correspond to the continuum ${}^{2}{A}^{\ensuremath{'}\ensuremath{'}}$ and ${}^{2}{A}^{\ensuremath{'}}$ scattering symmetries, respectively, are identified. The former can be associated to the ${}^{2}{B}_{1}$ shape resonance in formaldehyde located at around 2.5 eV, whereas the latter can be related to the ${}^{2}E$ resonance in ammonia at about 10 eV. Such correspondence is very interesting and so supports the investigation on electron interaction with small building blocks, instead of with larger biomolecules.

Communication: The origin of rotational enhancement effect for the reaction of H2O+ + H2 (D2)

We have measured the absolute integral cross sections (σ's) for H3O(+) formed by the reaction of rovibrationally selected H2O(+)(X(2)B1; v1 (+)v2 (+)v3 (+) = 000; N(+) K a (+) K c (+) = 000, 111, and 211) ion with H2 at the center-of-mass collision energy (Ecm) range of 0.03-10.00 eV. The σ(000), σ(111), and σ(211) values thus obtained reveal rotational enhancements at low Ecm < 0.50 eV, in agreement with the observation of the previous study of the H2O(+)(X(2)B1) + D2 reaction. This Communication presents important progress concerning the high-level ab initio quantum calculation of the potential energy surface for the H2O(+)(X(2)B1) + H2 (D2) reactions, which has provided valuable insight into the origin of the rotational enhancement effect. Governed by the charge and dipole-induced-multipole interactions, the calculation shows that H2 (D2) approaches the H end of H2O(+)(X(2)B1) in the long range, whereas chemical force in the short range favors the orientation of H2 (D2) toward the O side of H2O(+). The reorientation of H2O(+) reactant ion facilitated by rotational excitation thus promotes the H2O(+) + H2 (D2) reaction along the minimum energy pathway, rendering the observed rotational enhancement effects. The occurrence of this effect at low Ecm indicates that the long range charge and dipole-induced-multipole interactions of the colliding pair play a significant role in the dynamics of the exothermic H2O(+) + H2 (D2) reactions.

Cross sections for electron collisions with dimethyl ether

We report a joint theoretical-experimental investigation of electron collision with dimethyl ether (DME) in the low- and intermediate-energy ranges. Experimental absolute differential, integral, and momentum-transfer cross sections for elastic ${e}^{\ensuremath{-}}$-DME scattering are reported in the 100--1000 eV energy range. Our measurements were performed using a crossed electron-beam--molecular-beam geometry. The angular distribution of the scattered electrons was converted to absolute cross section using the relative flow technique. Theoretically, elastic differential, integral, and momentum-transfer cross sections, as well as the grand-total and total absorption cross sections for electron collision with DME are calculated in the 1--1000 eV energy range. A single-center-expansion technique combined with the Pad\'e approximant method is used in our calculations. A comparison between the present experimental and theoretical data shows very good agreement. Moreover, comparison with theoretical and experimental data for ${e}^{\ensuremath{-}}$-ethanol (an isomer of DME) scattering shows interesting isomeric effects.

The translational, rotational, and vibrational energy effects on the chemical reactivity of water cation H2O+(X 2B1) in the collision with deuterium molecule D2

By employing the newly established vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) double quadrupole-double octopole ion guide apparatus, we have examined the translational, rotational, and vibrational energy effects on the chemical reactivity of water cation H2O(+)(X(2)B1) in the collision with deuterium molecule D2. The application of a novel electric-field pulsing scheme to the VUV laser PFI-PI ion source has enabled the preparation of a rovibrationally selected H2O(+)(X(2)B1; v1 (+)v2 (+)v3 (+); N(+) K a+Kc+) ion beam with not only high internal-state selectivity and high intensity but also high translational energy resolution. Despite the unfavorable Franck-Condon factors, we are able to prepare the excited vibrational states (v1 (+)v2 (+)v3 (+))=(100) and (020) along with the (000) ground vibrational state, for collisional studies, where v1 (+), v2 (+), and v3 (+) represent the symmetric stretching, bending, and asymmetric stretching modes of H2O(+)(X(2)B1). We show that a range of rotational levels from N(+) K a+Kc+ = 000 to 322, covering a rotational energy range of 0-200 cm(-1) of these vibrational states, can also be generated for absolute integral cross section (σ) measurements at center-of-mass collision energies (Ecms) from thermal energies to 10.00 eV. The Ecm dependences of the σ values are consistent with the prediction of the orbiting model, indicating that translational energy significantly hinders the chemical reactivity of H2O(+)(X(2)B1). Rotational enhancements are observed at Ecm < 0.30 eV for all the three vibrational states, (000), (100), and (020). While the σ values for (100) are found to be only slightly below those for (000), the σ values for (020) are lower than those for (000) and (100) by up to 20% at Ecm ≤ 0.20 eV, indicative of vibrational inhibition at low Ecm by excitation of the (020) mode. Rationalizations are proposed for the observed rotational enhancements and the bending vibrational inhibition. Rigorous theoretical calculations are needed to interpret the wealth of rovibrationally selected cross sections obtained in the present study.

A joint theoretical and experimental study for elastic electron scattering from 1,4-dioxane

We present results of measurements and calculations of elastic electron scattering from 1,4-dioxane in the energy range of 0-1000 eV. Absolute differential and integral elastic cross sections have been measured using a crossed electron-molecule beam spectrometer and the relative flow technique, at four energies in the 10-30 eV range and for scattered electrons in the angular range 20°-129°. The measured cross sections are compared with results from R-matrix computations, at the static exchange plus polarization level, calculated at energies between 0-20 eV, and with calculations employing the independent atom model with the screening corrected additivity rule (IAM-SCAR). Those latter computations were conducted at energies between 1 and 1000 eV. Agreement between the measured and R-matrix cross sections was typically found to be good at all common energies, whereas agreement with IAM-SCAR was satisfactory only at 30 eV. To the best of our knowledge, the present results are the first absolute data to be published in the literature for this scattering system.

Absolute differential and integral cross sections for CCl4 molecules by low energy electron impact

We report absolute differential cross sections (DCSs) and integral cross sections (ICSs) for elastic electron scattering with CCl4 molecules in the energy range of 1.5-100eV. In addition, the experimental DCSs are compared with the results from theoretical calculations based on the Schwinger multichannel method with norm-conserving pseudopotentials.