Library

Notes: Absolute total cross sections for the reactions, O+(4S) + H2(X 1Σ+g)→O+H+2 [reaction (1)] and O+H+H+ [reaction (2)] have been measured in the center-of-mass collision energy (Ec.m.) range of 1.33–22.22 eV. The appearance energies for H+2 (1.70±0.10 eV) and H+ (4.50±0.10 eV) are in excellent agreement with the thermochemical thresholds for reactions (1) and (2), respectively. At Ec.m. higher than approximately 9 eV, the total cross sections for reactions (1) and (2) are greater than that for the exothermic channel forming OH++H.

Notes: A detailed three-dimensional quantum mechanical study of the (Ar+H2)+ system along the energy range 0.4 eV≤Etot≤1.65 eV is presented. The main difference between this new treatment and the previously published one [J. Chem. Phys. 87, 465 (1987)] is the employment of a new version of the reactive infinite-order sudden approximation (IOSA), which is based on the ordinary inelastic IOSA carried out for an optical potential. In the numerical treatment we include three surfaces (only two were included in the previous treatment), one which correlates with the Ar+H+2 system and two which correlate with the two spin states of Ar+(2Pj); j=3/2,1/2. The results are compared with both trajectory-surface-hopping calculations and with experiments. In most cases, very good agreement is obtained.

Notes: Absolute total cross sections for the reactions, Ar+(2P3/2,1/2)+N2→N++N+Ar [reaction (1)] and ArN++N [reaction (2)], have been measured in the center-of-mass collision energy (Ec.m.) range of 6.2–123.5 eV. The appearance energy for the formation of N+ (Ec.m.=8.65±0.21 eV) is in agreement with the thermochemical threshold for reaction (1). The comparison of the collision energy dependence of the N+ cross section with the photoionization efficiency spectrum of N+ from N2 suggests that the predissociative multielectron states of N+2, C˜ 2Σ+u, F˜ 2Σ+g, G˜ 2Σ+g, and 2Σ+g (2σg)−1, which are responsible for the dissociative photoionization of N2, also play a role in the formation of N+ via reaction (1). Product ArN+ ions of reaction (2) are only observed in the Ec.m. range of 8.2–41.2 eV. At Ec.m. slightly above the thermochemical thresholds of reactions (1) and (2), the majority of ArN+ and N+ ions are scattered backward and forward with respect to the center-of-mass velocity of reactant Ar+, respectively. This observation is rationalized by a charge transfer predissociation mechanism which involves the formation of ArN+ and N+ ions via nearly collinear Ar+-N-N collision configurations at Ec.m. near the thresholds of reactions (1) and (2). At Ec.m.≥11 eV, more than 92% of the charge transfer product N+2 ions are found to be slow ions formed mostly by the long-range electron jump mechanism.

Notes: The reaction between oxygen ions and nitrogen molecules is studied by using tandem photoionization mass spectroscopy. This reaction is pertinent to the study of reaction occuring in the inosphere. (AIP)

Notes: Total state-selected and state-to-state absolute cross sections for the reactions Ar+(2P3/2,1/2)+H2(X,v=0)→Ar (1S0)+H+2(X˜,v') [reaction (1)], ArH++H [reaction (2)], and H++H+Ar [reaction (3)] have been measured in the center-of-mass collision energy Ec.m. range of 0.24–19.1 eV. Absolute spin–orbit state transition total cross sections (σ3/2→1/2,σ1/2→3/2) for the collisions of Ar+(2P3/2,1/2) with H2 at Ec.m.=1.2–19.1 eV have been obtained.The measured state-selected cross sections for reaction (1) [σ3/2,1/2(H+2)] reveal that at Ec.m.≤5 eV, σ1/2(H+2) is greater than σ3/2(H+2), while the reverse is observed at Ec.m.≥7 eV. The total state-to-state absolute cross sections for reaction (1) (σ3/2,1/2→v') show unambiguously that in the Ec.m. range of 0.16–3.9 eV the dominant product channel formed in the reaction of Ar+(2P1/2)+H2(X,v=0) is H+2(X˜,v'=2)+Ar. These observations support the conclusion that at low Ec.m. the outcome of charge transfer collisions is governed mostly by the close energy resonance effect. However, at sufficiently high Ec.m.(〉6 eV) the charge transfer of Ar+(2P3/2)+H2 is favored compared to that of Ar+(2P1/2)+H2.The relative values measured for X1/2→v'[≡σ1/2→v'/σ1/2 (H+2)] are in good accord with those predicted from calculations using the state-to-state cross sections for the H+2(X˜,v'=0–4)+Ar charge transfer reaction and the relation based on microscopic reversibility. The experimental values for X3/2→v'[≡σ3/2→v'/σ3/2 (H+2)] and those predicted using the microscopic reversibility argument are also in fair agreement. The spin–orbit effect for the cross section of reaction (2) [σ3/2,1/2(ArH+)] is significantly less than that for reaction (1). Both σ3/2(ArH+) and σ1/2(ArH+) decrease rapidly as Ec.m. is increased, and become essentially identical at Ec.m. ≈3.8 eV. The cross sections for reaction (3) observed in the Ec.m. range of 2.5–12 eV are ≤3% of σ3/2,1/2(H+2).The onset for the formation of H+ by reaction (3) is consistent with the thermochemical threshold. The values for σ3/2→1/2 and σ1/2→3/2 observed here are nearly a factor of 2 greater than those measured by the energy loss spectroscopic method. However, the kinetic energy dependencies for σ3/2→1/2 and σ1/2→3/2 are in accord with the previous measurements. Theoretical cross sections for the charge transfer and spin–orbit state transition reactions are calculated at Ec.m.=19.3 eV using the nonreactive infinite-order sudden approximation for comparison with experimental values.

Notes: Absolute spin–orbit state-selected total cross sections for the reactions, Ar+(2P3/2,1/2)+O2→O+2+Ar [reaction (1)], O++O+Ar [reaction (2)], and ArO++O [reaction (3)], have been measured in the center-of-mass collision energy (Ec.m.) range of 0.044–133.3 eV. Absolute spin–orbit state transition total cross sections for the Ar+(2P3/2,1/2)+O2 reaction at Ec.m.=2.2–177.6 eV have also been examined. The appearance energies for the formation of O+ (Ec.m.=2.9±0.2 eV) and ArO+ (2.2±0.2 eV) are in agreement with the thermochemical thresholds for reactions (2) and (3), respectively. The cross sections for O+2, O+, and ArO+ depend strongly on Ec.m. and the spin–orbit states of Ar+, suggesting that reactions (1)–(3) are governed predominantly by couplings between electronic potential energy surfaces arising from the interactions of Ar+(2P3/2)+O2, Ar+(2P1/2)+O2, and O+2+Ar.In the Ec.m. range of 6.7–22.2 eV, corresponding to the peak region of the O+ cross section curve, the cross sections for O+ are ≥50% of those for O+2. The production of O+ by reaction (2) is interpreted to be the result of predissociation of O+2 in excited states formed initially by reaction (1). The formation of charge transfer O+2(a˜ 4Πu) has been probed by the charge transfer reaction O+2(a˜ 4Πu)+Ar. The results indicate that in the Ec.m. range of 0.4–3.0 eV charge transfer product O+2 ions are formed mainly in the O+2(a˜ 4Πu) state. Experimental evidence is found supporting the conclusion that the vibrational distributions of O+2(a˜ 4Πu) formed in reaction (1) and by photoionization of O2 in the energy range between the O+2(a˜ 4Πu, v=0) and O+2(A˜ 2Πu, v=0) thresholds are similar.The population of O+(4S) formed by reaction (2) has also been measured by the reaction O+(4S)+N2→NO++N. In the Ec.m. range of 3–44 eV, product O+ ions of reaction (2) are shown to be dominantly in the O+(4S) ground state. At Ec.m.≥14 eV, the retarding potential energy analysis for O+2 shows that more than 98% of the charge transfer O+2 ions are slow ions formed mostly by the long-range electron jump mechanism. Product ArO+ ions are observed only in the Ec.m. range of 2.2–26.6 eV. At Ec.m. slightly above the thermochemical thresholds of reactions (2) and (3), the overwhelming majority of ArO+ and O+ ions are scattered backward and forward with respect to the c.m. velocity of reactant Ar+, respectively. This observation is rationalized by a charge transfer predissociation mechanism which involves the formation of ArO+ and O+ via nearly collinear Ar+–O–O collision configurations at Ec.m. near the thresholds of reactions (2) and (3).

Notes: Absolute spin–orbit state-selected total cross sections for the reactions, Ar+(2P3/2,1/2)+CO2→CO+2+Ar [reaction (1)], CO++O+Ar [reaction (2)], O++CO+Ar [reaction (3)], C++2O+Ar [reaction (4)], ArC++2O [reaction (5)], ArO++CO [reaction (6)], and ArCO++O [reaction (7)] have been measured in the center-of-mass collision energy (Ec.m.) range of 0.26–131 eV. The ratio of the charge-transfer cross section due to Ar+(2P1/2) to that associated with Ar+(2P3/2) varies in the range of 0.5–0.8. The appearance energies observed for CO+ (Ec.m.=4.2±0.5 eV), O+ (Ec.m.=3.7±0.5 eV), and C+ (Ec.m.=12.6±0.5 eV) are in agreement with the thermochemical thresholds for reactions (2), (3), and (4), respectively. The comparison of the absolute cross sections for CO+, O+, and C+ from CO2 by photoionization and by dissociative charge transfer [reactions (2)–(4)] is made. The kinetic-energy analysis of product CO+2, CO+, O+, C+, ArO+, and ArC+ suggests that reactions (2)–(7) proceed via a charge-transfer predissociation mechanism. This experiment, together with the previous studies of Ar+(2P3/2,1/2)+N2(O2,CO), supports the conclusion that product ions formed by dissociative photoionization are also produced by dissociative charge transfer. We find that the absolute cross sections for product ions formed in the dissociative charge-transfer processes [reactions (2)–(4)] are substantially greater than those formed in the dissociative photoionization of CO2, a finding consistent with the general observation that photoionization cross sections are significantly smaller than charge-transfer cross sections.The relative cross sections for CO+, O+, and C+ formed by reactions (2)–(4) are also found to be different from those for photoionization of CO2. This difference is attributed to the anisotropic interaction potential surface responsible for the Ar+(2P3/2,1/2)+CO2 reactions.

Notes: Absolute spin–orbit state-selected total cross sections for the reactions, Ar+(2P3/2,1/2)+CO→CO++Ar [reaction (1)], C++O+Ar [reaction (2)], O++C+Ar [reaction (3)], and ArC++O [reaction (4)], have been measured in the center-of-mass collision energy (Ec.m.) range of 0.04–123.5 eV. Absolute spin–orbit state transition total cross sections for the Ar+(2P3/2,1/2)+CO reactions at Ec.m. have also been obtained. The appearance energies (AE) for C+(Ec.m.=6.6±0.4 eV) and O+(Ec.m.=8.6±0.4 eV) are in agreement with the thermochemical thresholds for reactions (2) and (3), respectively. The observed AE for reaction (4) yields a lower bound of 0.5 eV for the ArC+ bond dissociation energy. The kinetic energy dependence of the absolute cross sections and the retarding potential analysis of the product ions support that ArC+, C+, and O+ are formed via a charge transfer predissociation mechanism, similar to that proposed to be responsible for the formation of O+ (N+) and ArO+ (ArN+) in the collisions of Ar+(2P3/2,1/2)+O2(N2).