Dissociative recombination of N2H+ ions with electrons in the temperature range of 80-350 K.

Recombination of N2H+ ions with electrons was studied using a stationary afterglow with a cavity ring-down spectrometer. We probed in situ the time evolutions of number densities of different rotational and vibrational states of recombining N2H+ ions and determined the thermal recombination rate coefficients for N2H+ in the temperature range of 80-350 K. The newly calculated vibrational transition moments of N2H+ are used to explain the different values of recombination rate coefficients obtained in some of the previous studies. No statistically significant dependence of the measured recombination rate coefficient on the buffer gas number density was observed.

Velocity distribution functions for O+(4S3/2) ions drifting in helium and cross section for reaction of O+(4S3/2) with N2(v = 0).

The Gram-Charlier method for solving the Boltzmann equation is used to compute velocity distribution functions for O+(4S3/2) ions drifting under the influence of an electric field through helium or argon gas containing small amounts of N2. This allows us to reassess the accuracy of the commonly used reaction cross section for the O+(4S3/2) +N2 reaction, perhaps the most important reaction in the upper ionosphere. It is found that the cross sections that were derived from flow-drift measurements are in considerable error for relative kinetic energies of 0.3-3 eV between the reacting species. Using the best available transport theory, flow-drift tube data of the reaction rate coefficient are inverted to obtain a better cross section.

Binary and ternary recombination of H2D(+) and HD2(+) ions with electrons at 80 K.

The recombination of deuterated trihydrogen cations with electrons has been studied in afterglow plasmas containing mixtures of helium, argon, hydrogen and deuterium. By monitoring the fractional abundances of H3(+), H2D(+), HD2(+) and D3(+) as a function of the [D2]/[H2] ratio using infrared absorption observed in a cavity ring down absorption spectrometer (CRDS), it was possible to deduce effective recombination rate coefficients for H2D(+) and HD2(+) ions at a temperature of 80 K. From pressure dependences of the measured effective recombination rate coefficients the binary and the ternary recombination rate coefficients for both ions have been determined. The inferred binary and ternary recombination rate coefficients are: αbinH2D(80 K) = (7.1 ± 4.2) × 10(-8) cm(3) s(-1), αbinHD2(80 K) = (8.7 ± 2.5) × 10(-8) cm(3) s(-1), KH2D(80 K) = (1.1 ± 0.6) × 10(-25) cm(6) s(-1) and KHD2(80 K) = (1.5 ± 0.4) × 10(-25) cm(6) s(-1).

Transport coefficients of He(+) ions in helium.

This paper demonstrates that the transport coefficients of (4)He(+) in (4)He can be calculated over wide ranges of E/N, the ratio of the electrostatic field strength to the gas number density, with the same level of precision as can be obtained experimentally if sufficiently accurate potential energy curves are available for the X(2)Σu (+) and A(2)Σg (+) states and one takes into account resonant charge transfer. We start by computing new potential energy curves for these states and testing their accuracy by calculating spectroscopic values for the separate states. It is established that the potentials obtained by extrapolation of results from d-aug-cc-pVXZ (X = 6, 7) basis sets using the CASSCF+MRCISD approach are each in exceptionally close agreement with the best potentials available and with experiment. The potentials are then used in a new computer program to determine the semi-classical phase shifts and the transport cross sections, and from these the gaseous ion transport coefficients are determined. In addition, new experimental values are reported for the mobilities of (4)He(+) in (4)He at 298.7 K, as a function of E/N, where careful consideration is given to minimizing various sources of uncertainty. Comparison with previously measured values establishes that only one set of previous data is reliable. Finally, the experimental and theoretical ion transport coefficients are shown to be in very good to excellent agreement, once corrections are applied to account for quantum-mechanical effects.

Flowing-afterglow study of electron-ion recombination of para-H3(+) and ortho-H3(+) ions at temperatures from 60 K to 300 K.

Detailed measurements employing a combination of a cryogenic flowing afterglow with Langmuir probe (Cryo-FALP II) and a stationary afterglow with near-infrared absorption spectroscopy (SA-CRDS) show that binary electron recombination of para-H3(+) and ortho-H3(+) ions occurs with significantly different rate coefficients, (p)αbin and (o)αbin, especially at very low temperatures. The measurements cover temperatures from 60 K to 300 K. At the lowest temperature of 60 K, recombination of para-H3(+) is at least three times faster than that of ortho-H3(+) ((p)αbin=(1.8±0.4)×10(-7) cm(3) s(-1) vs. (o)αbin=(0-0 (+5))×10(-8) cm(3) s(-1)).

Mutual neutralization of atomic rare-gas cations (Ne(+), Ar(+), Kr(+), Xe(+)) with atomic halide anions (Cl(-), Br(-), I(-)).

We report thermal rate coefficients for 12 reactions of rare gas cations (Ne(+), Ar(+), Kr(+), Xe(+)) with halide anions (Cl(-), Br(-), I(-)), comprising both mutual neutralization (MN) and transfer ionization. No rate coefficients have been previously reported for these reactions; however, the development of the Variable Electron and Neutral Density Attachment Mass Spectrometry technique makes it possible to measure the difference of the rate coefficients for pairs of parallel reactions in a Flowing Afterglow-Langmuir Probe apparatus. Measurements of 18 such combinations of competing reaction pairs yield an over-determined data set from which a consistent set of rate coefficients of the 12 MN reactions can be deduced. Unlike rate coefficients of MN reactions involving at least one polyatomic ion, which vary by at most a factor of ∼3, those of the atom-atom reactions vary by at least a factor 60 depending on the species. It is found that the rate coefficients involving light rare-gas ions are larger than those for the heavier rare-gas ions, but the opposite trend is observed in the progression from Cl(-) to I(-). The largest rate coefficient is 6.5 × 10(-8) cm(3) s(-1) for Ne(+) with I(-). Rate coefficients for Ar(+), Kr(+), and Xe(+) reacting with Br2 (-) are also reported.

Communication: Transfer ionization in a thermal reaction of a cation and anion: Ar+ with Br- and I-.

We present experimental evidence that reactions of argon cations Ar(+) with the halogen anions Br(-) and I(-) do not occur exclusively by mutual neutralization, but also produce the cations Br(+) or I(+) ions by transfer ionization (TI). The experiments were carried out in flowing-afterglow plasmas at gas temperatures between and 300 and 500 K, and employed a variant of the Variable Electron and Neutral Density Attachment Mass Spectrometry method. The measured TI rate coefficients are 1.9 ± 0.6 × 10(-9) cm(3) s(-1) and 1.1 ± (0.3)(0.8) × 10(-9) cm(3) s(-1) for the Br(-) and I(-) reactions, respectively. We find that the TI rate coefficients decline with temperature as T(-0.5) to T(-1). No indication of TI was found in the reaction with Cl(-), where it is endoergic.

Flowing afterglow measurements of the density dependence of gas-phase ion-ion mutual neutralization reactions.

We have studied the dependence of several ion-ion mutual neutralization (MN) reactions on helium density in the range from 1.6 × 10(16) to 1.5 × 10(17) cm(-3) at 300 K, using the Variable Electron and Neutral Density Attachment Mass Spectrometry method. The rate coefficients of the reactions Ar(+) + Br2(-), Ar(+) + SF6(-), and Ar(+) + C7F14(-) were found to be independent of gas density over the range studied, in disagreement with earlier observations that similar MN reactions are strongly enhanced at the same gas densities. The cause of the previous enhancement with density is traced to the use of "orbital-motion-limit" theory to infer ion densities from the currents collected by ion-attracting Langmuir probes in a region where it is not applicable.

Kinetic processes in recombining H3+ plasmas.

Recombination in plasmas containing H(3)(+) ions occurs not only by binary recombination but also by third-body-assisted mechanisms, the principal subject of this contribution. Third-body effects on recombination are of interest for model calculations of hydrogen discharges, their spectral emissions and the inference of binary recombination coefficients from plasma afterglow data.

Binary and ternary recombination of para-H3(+) and ortho-H3(+) with electrons: state selective study at 77-200 K.

Measurements in H(3)(+) afterglow plasmas with spectroscopically determined relative abundances of H(3)(+) ions in the para-nuclear and ortho-nuclear spin states provide clear evidence that at low temperatures (77-200 K) para-H(3)(+) ions recombine significantly faster with electrons than ions in the ortho state, in agreement with a recent theoretical prediction. The cavity ring-down absorption spectroscopy used here provides an in situ determination of the para/ortho abundance ratio and yields additional information on the translational and rotational temperatures of the recombining ions. The results show that H(3)(+) recombination with electrons occurs by both binary recombination and third-body (helium) assisted recombination, and that both the two-body and three-body rate coefficients depend on the nuclear spin states. Electron-stabilized (collisional-radiative) recombination appears to make only a small contribution.

Interaction potentials of uranium cations with rare gases (RG) and transport of U+ in RG (RG = He, Ne, Ar, Kr, and Xe).

We present accurate interaction potentials for uranium cations interacting with the rare gases (RG = He-Rn), using effective core potentials that include a description of the 5f electrons in the case of uranium, and justify this approximation in some detail. From these interaction potentials, spectroscopic parameters are derived for the U(+)-RG complexes. We also employ the potentials to calculate transport coefficients for U(+) moving through a bath of each RG. In the case of U(+) in He, we are able to compare with previous experimentally determined mobility values, and we make some minor corrections to the previously reported data; this revised data is presented.

Interaction potentials, spectroscopy, and transport properties of Ne(+)-He and He(+)-Ne.

High-level ab initio potential energy curves are calculated for the lowest few states of the [He-Ne](+) complex. RCCSD(T) calculations are employed with large basis sets (up to sextuple-zeta), including extrapolation to the basis set limit, taking account of spin-orbit coupling. In addition, core-valence correlation and multireference effects are investigated. We calculate spectroscopic parameters and compare these to experimentally determined values, to other high-level ab initio results, and to results from potentials that are fitted to experimental data. We present the results of new measurements of the mobility of Ne(+) in He. We also calculate mobilities for Ne(+) in He, and He(+) in Ne, from our potentials and from recent fitted potentials; and compare the calculated and experimental mobilities graphically and statistically.

Transport of O+ through argon gas.

New experimental and theoretical results are presented that address the movement of O+ ions through argon gas. On the experimental front, improved ion mobility results are presented. These results confirm the presence of the oft-cited mobility minimum as a function of electrostatic field strength at room temperature. On the theoretical side, high-level ab initio potential energy curves are calculated for the Ar-O+ system and, from these, transport properties are calculated and compared to experiment. A crossing between the lowest 2Pi curve and the ground state 4Sigma(-) curve near the minimum of each potential becomes an avoided crossing on the inclusion of spin-orbit coupling. It is shown that the more appropriate potential for the description of the motion of O+(4S degree) through Ar at the energies of interest is the diabatic potential, neglecting fine structure. By using an improved 4Sigma(-) potential, agreement with the mobility measurements is obtained for low and intermediate electrostatic field strengths, although small discrepancies remain for high field strengths. The appropriate choice of diabatic or adiabatic potentials is also considered for related systems of interest: He-O+, Ne-O+, and Rg-O(-) (Rg=He,Ne,Ar).

Interaction potential and transport properties of NeO(+).

The results of both experimental and theoretical studies of the mobility of O(+) in Ne are reported. Errors in the experiments have been carefully assessed, allowing the obtained data to serve as stringent tests of the ab initio potentials. These potentials were calculated using the RCCSD(T) method, employing basis sets of quintuple-zeta quality. Curves were calculated for the lowest (4)Sigma(-) state [arising from O(+)((4)S) interacting with Ne] and for the (2)Pi state [arising from O(+)((2)D) interacting with Ne]. Then, the effects of spin-orbit coupling were incorporated by using the Breit-Pauli operator. The resulting ground state (Omega=32) of NeO(+) gives mobility values in good agreement with experiment at all field strengths. Values of spectroscopic quantities for the ground electronic state of NeO(+) are also presented.

Yield of excited CO molecules from dissociative recombination of HCO+ and HOC+ ions with electrons.

The authors have investigated CO band emissions arising from the dissociative recombination of HCO(+) and HOC(+) ions with thermal electrons in a flowing afterglow plasma. The quantitative analysis of the band intensities showed that HCO(+) recombination forms the long-lived CO(a (3)Pi) state with a yield of 0.23+/-0.12, while HOC(+) recombination favors formation of CO(a' (3)Sigma(+)) and CO(d (3)Delta) with a combined yield of greater than 0.4. The observed vibrational distribution for the CO(a) state reproduces theoretical predictions quite well. The vibrational distributions for CO(a') and CO(d) are, in part, inverted, presumably as a consequence of a change in CO equilibrium bond length during recombination. The observations are compatible with current knowledge of the potential surfaces of states of HCO and HCO(+).

Yield of electronically excited CN molecules from the dissociative recombination of HNC+ with electrons.

The authors have studied CN(B-X) and CN(A-X) emissions produced by the dissociative recombination of HNC+ ions with thermal electrons in a flowing afterglow experiment. A separate drift tube study showed that the reaction Ar(+)+HCN, the precursor reaction used in the flow-tube experiment, produces predominantly HNC+ rather than the more energetic HCN+ isomer. Models simulating the ion-chemical processes, diffusion, and gas mixing in the afterglow plasma were fitted to observed position dependent CN(A-X) and CN(B-X) band intensities. Absolute yields of CN(B) and CN(A) were then obtained by comparing the CN band intensities to those of CO bands produced by recombination of CO(2) (+) ions. It was concluded that the 300 K recombination coefficient of HNC+ is close to 2 x 10(-7) cm(3) s(-1), that CN(B) is formed with a yield of 0.22+/-0.08 and CN(A) with a yield of 0.14+/-0.05. By comparison to synthetic spectra, the rotational temperature of CN(B) was estimated to be approximately 2500 K. It was also found that recombination produces CN(B) and CN(A) with far greater vibrational excitation than would be expected from the "impulse model" of Bates [Mon. Not. R. Astron. Soc. 263, 369 (1993)].

Mobility of O+ in He and interaction potential of HeO+.

New experimental measurements are reported for the mobility of O(+) ions in He gas at 300 K. The accuracy of these new values is estimated as +/-2.5%, which allows them to serve as a stringent test of a new ab initio potential that we have calculated using the RCCSD(T) method. We employed the aug-cc-pV5Z basis set with counterpoise corrections and took spin-orbit coupling into account. The present experimental values lie below the calculated ones, but the difference becomes statistically significant only at moderate and high values of the ratio of the electric field strength to the gas number density; even there they are only marginally significant.

Yield of electronically excited N2 molecules from the dissociative recombination of N2H+ with e-.

Quantitative spectroscopic observations of the N2 first positive band system (N2(B 3Pig-A 3Sigmau+))/electron in a recombining N2H+ flowing-afterglow plasma indicate that a substantial fraction of the product N2 molecules are formed in one or more of the low-lying triplet states, B 3Pig, A 3Sigmau+, and W 3Deltau. The total measured N2(B-A) emission intensity from N2(B,v' > or = 1) is equivalent to a yield of (19 +/- 8)%. The effect of rapid collision-induced transitions between states of the triplet manifold is discussed..