Dissociative Recombination Rate Research Articles

Dissociative recombination of NS+ in collision with slow electrons

Cross sections and rate coefficients for the dissociative recombination (DR) of the NS+ ion induced by collisions with low-energy electrons are reported for temperatures between 10 and 1000 K, relevant to a large range of interstellar cloud temperatures. Uncertainties are discussed for these rates. Comparisons are made with DR rates for the isovalent NO+ molecular ion which are found to be much faster. The present findings lead to a moderate dissociative reaction rate coefficient, smaller by a factor of 2 than the current estimates reported in the different kinetic databases for a temperature of 10 K. We consider that our rate coefficients obtained through multichannel quantum defect theory for NS+ are likely to be better than those displayed in the different kinetic databases.

Discovery of thiofulminic acid with the QUIJOTE line survey: A study of the isomers of HNCS and HNCO in TMC-1

We present the first detection of HCNS (thiofulminic acid) in space with the QUIJOTE line survey in the direction of TMC-1. We performed a complete study of the isomers of CHNS and CHNO, including NCO and NCS. The derived column densities for HCNS, HNCS, and HSCN are (9.0 ± 0.5) × 109, (3.2 ± 0.1) × 1011, and (8.3 ± 0.4) × 1011 cm−2, respectively. The HNCS/HSCN abundance ratio is 0.38. The abundance ratios HNCO/HNCS, HCNO/HCNS, HOCN/HSCN, and NCO/NCS are 34 ± 4, 8.3 ± 0.7, 0.18 ± 0.03, and 0.78 ± 0.07, respectively. These ratios cannot be correctly reproduced by our gas-phase chemical models, which suggests that formation paths for these species are missing, and/or that the adopted dissociative recombination rates for their protonated precursors have to be revised. The isotopologues H15NCO, DNCO, HN13CO, DCNO, H34SCN, and DSCN have also been detected with the ultrasensitive QUIJOTE line survey.

Dissociative Recombination of Rotationally Cold OH+ and Its Implications for the Cosmic Ray Ionization Rate in Diffuse Clouds

Observations of OH+ are used to infer the interstellar cosmic ray ionization rate in diffuse atomic clouds, thereby constraining the propagation of cosmic rays through and the shielding by interstellar clouds, as well as the low energy cosmic ray spectrum. In regions where the H2-to-H number density ratio is low, dissociative recombination (DR) is the dominant destruction process for OH+ and the DR rate coefficient is important for predicting the OH+ abundance and inferring the cosmic ray ionization rate. We have experimentally studied DR of electronically and vibrationally relaxed OH+ in its lowest rotational levels, using an electron–ion merged-beams setup at the Cryogenic Storage Ring. From these measurements, we have derived a kinetic temperature rate coefficient applicable to diffuse cloud chemical models, i.e., for OH+ in its electronic, vibrational, and rotational ground level. At typical diffuse cloud temperatures, our kinetic temperature rate coefficient is a factor of ∼5 times larger than the previous experimentally derived value and a factor of ∼33 times larger than the value calculated by theory. Our combined experimental and modeling results point to a significant increase for the cosmic ray ionization rate inferred from observations of OH+ and H2O+, corresponding to a geometric mean of (6.6 ± 1.0) × 10−16 s−1, which is more than a factor of 2 larger than the previously inferred values of the cosmic ray ionization rate in diffuse atomic clouds. Combined with observations of diffuse and dense molecular clouds, these findings indicate a greater degree of cosmic ray shielding in interstellar clouds than has been previously inferred.

Near-thermo-neutral electron recombination of titanium oxide ions.

While the dissociative recombination (DR) of ground-state molecular ions with low-energy free electrons is generally known to be exothermic, it has been predicted to be endothermic for a class of transition-metal oxide ions. To understand this unusual case, the electron recombination of titanium oxide ions (TiO+) with electrons has been experimentally investigated using the Cryogenic Storage Ring. In its low radiation field, the TiO+ ions relax internally to low rotational excitation (≲100 K). Under controlled collision energies down to ∼2 meV within the merged electron and ion beam configuration, fragment imaging has been applied to determine the kinetic energy released to Ti and O neutral reaction products. Detailed analysis of the fragment imaging data considering the reactant and product excitation channels reveals an endothermicity for the TiO+ dissociative electron recombination of (+4 ± 10) meV. This result improves the accuracy of the energy balance by a factor of 7 compared to that found indirectly from hitherto known molecular properties. Conversely, the present endothermicity yields improved dissociation energy values for D0(TiO) = (6.824 ± 0.010)eV and D0(TiO+) = (6.832 ± 0.010)eV. All thermochemistry values were compared to new coupled-cluster calculations and found to be in good agreement. Moreover, absolute rate coefficients for the electron recombination of rotationally relaxed ions have been measured, yielding an upper limit of 1 × 10-7 cm3 s-1 for typical conditions of cold astrophysical media. Strong variation of the DR rate with the TiO+ internal excitation is predicted. Furthermore, potential energy curves for TiO+ and TiO have been calculated using a multi-reference configuration interaction method to constrain quantum-dynamical paths driving the observed TiO+ electron recombination.

Experimental Determination of the Dissociative Recombination Rate Coefficient for Rotationally Cold CH+ and Its Implications for Diffuse Cloud Chemistry

Observations of CH+ are used to trace the physical properties of diffuse clouds, but this requires an accurate understanding of the underlying CH+ chemistry. Until this work, the most uncertain reaction in that chemistry was dissociative recombination (DR) of CH+. Using an electron–ion merged-beams experiment at the Cryogenic Storage Ring, we have determined the DR rate coefficient of the CH+ electronic, vibrational, and rotational ground state applicable for different diffuse cloud conditions. Our results reduce the previously unrecognized order-of-magnitude uncertainty in the CH+ DR rate coefficient to ∼20% and are applicable at all temperatures relevant to diffuse clouds, ranging from quiescent gas to gas locally heated by processes such as shocks and turbulence. Based on a simple chemical network, we find that DR can be an important destruction mechanism at temperatures relevant to quiescent gas. As the temperature increases locally, DR can continue to be important up to temperatures of ∼600 K, if there is also a corresponding increase in the electron fraction of the gas. Our new CH+ DR rate-coefficient data will increase the reliability of future studies of diffuse cloud physical properties via CH+ abundance observations.

Dissociative Recombination of K2+ and Rb2+ in Diode-Pumped Alkali Lasers: Potential Energy Curves and Atomic Products.

Dissociative recombination (DR) of K2+ and Rb2+ ions is one of the most important processes in K and Rb diode-pumped alkali lasers (DPALs) strongly affecting their power. We report on the calculations of potential energy curves of the K2+ and Rb2+ molecular ions and of the diabatic 1Σ+, 3Σ+, 1Δ, 3Δ, 1Π, 3Π, 1Φ, and 3Φ valence states of K2 and Rb2 that provide the routes for DR of the ions. These curves are required for subsequent calculations of DR rate constants. It was found that the most likely DR routes for K are along the dissociative states 61Σg+, 53Σu+, and 23Δu and for Rb only 61Σg+. The excited states of K atoms produced by DR are 42P and 52P. Most of the Rb atoms produced by DR are in the 62P excited state, while a small fraction of the atoms produced by the less likely routes along two states of Rb2 are in the 52P state. This conclusion contradicts the kinetic scheme for K and Rb DPAL proposed elsewhere, and thus the kinetic schemes of these DPALs should be modified according to the present results.

M3 electron density layer in the dayside ionosphere of Mars: Analysis of MAVEN ROSE observations

We investigate the characteristics of the topside M3 layer in the Martian dayside electron density profiles obtained from the Radio Occultation Science Experiment (ROSE) onboard the MAVEN spacecraft. M3 layer is a local enhancement in the electron density above the prominent ionospheric M2 peak. ROSE measurements have a wider latitudinal and solar zenith angle (SZA) coverage as compared to the spacecraft observations used by previous studies for characterizing the M3 layer. We analyzed 179 dayside (SZA <85∘) electron density profiles from July 2016 to December 2020. The analysis show that the typical altitude of M3 layer is ∼180 (±10) km, with a density of ∼8 (±3) x 103 cm−3, and occur ∼43 (±8) km above the M2 peak. These values are consistent with those reported by an earlier study using MGS RO data. The density of M3 layer seems to be insensitive to changes in SZA in the range of 55∘ to 85∘. The increasing trend in the M3 peak altitude with increasing SZA might be indicative of M3 forming at constant pressure levels, similar to M2. In the northern hemisphere, both the M3 peak density and altitude seem insensitive to latitudinal changes. The most commonly cited reasons for the production of the M3 layer are the enhancement in the electron temperature and the converging vertical plasma motion caused by the crustal magnetic field. Our simulations using a one-dimensional photochemical model suggest that decreased dissociative recombination rate due to electron temperature enhancements may not contribute to the formation of M3 layer. We conclude that the presence of crustal magnetic field also could not wholly explain the formation of M3 layer.

Dissociative Recombination of Cold HeH^{+} Ions.

The HeH^{+} cation is the simplest molecular prototype of the indirect dissociative recombination (DR) process that proceeds through electron capture into Rydberg states of the corresponding neutral molecule. This Letter develops the first application of our recently developed energy-dependent frame transformation theory to the indirect DR processes. The theoretical model is based on the multichannel quantum-defect theory with the vibrational basis states computed using exterior complex scaling of the nuclear Hamiltonian. The abinitio electronic R-matrix theory is adopted to compute quantum defects as functions of the collision energy and of the internuclear distance. The resulting DR rates are convolved over the beam energy distributions relevant to a recent experiment at the Cryogenic Storage Ring, giving good agreement between the experiment and the theory.

Evaluating Local Ionization Balance in the Nightside Martian Upper Atmosphere during MAVEN Deep Dip Campaigns

Abstract Combining the Mars Atmosphere and Volatile Evolution (MAVEN) measurements of atmospheric neutral and ion densities, electron temperature, and energetic electron intensity, we perform the first quantitative evaluation of local ionization balance in the nightside Martian upper atmosphere, a condition with the electron impact ionization (EI) of CO2 exactly balanced by the dissociative recombination (DR) of ambient ions. The data accumulated during two MAVEN Deep Dip (DD) campaigns are included: DD6 on the deep nightside with a periapsis solar zenith angle (SZA) of 165°, and DD3 close to the dawn terminator with a periapsis SZA of 110°. With the electron temperatures at low altitudes corrected for an instrumental effect pertaining to the MAVEN Langmuir Probe and Waves, a statistical agreement between the EI and DR rates is suggested by the data below 140 km during DD6 and below 180 km during DD3, implying that electron precipitation is responsible for the nightside Martian ionosphere under these circumstances and extra sources are not required. In contrast, a substantial enhancement in EI over DR is observed at higher altitudes during both campaigns, which we interpret as a signature of plasma escape down the tail.

Dissociative recombination of CH2NH2+: a crucial link with interstellar methanimine and Titan ammonia

Cross sections for dissociative recombination (DR) and vibrational excitation of the CH2NH + 2 ion in collisions with electrons are determined theoretically. The corresponding thermally averaged rate coefficients are computed and fitted to analytical formulas. The obtained DR rate coefficient is significantly smaller than the values recently employed in the photochemical models of the upper atmosphere of Titan, which has an important impact on the models that aim to reproduce the Titan ammonia abundance. On the other hand, the present results support the astrophysical models reproducing the abundance of the methanimine (CH2NH) detected in massive star formation regions. In these models, the CH2NH + 2 DR is a major route of formation of this molecule with a high prebiotic potential.

Theoretical study of ArH+ dissociative recombination and electron-impact vibrational excitation

Cross sections are presented for dissociative recombination and electron-impact vibrational excitation of the ArH+ molecular ion at electron energies appropriate for the interstellar environment. The R-matrix method is employed to determine the molecular structure data, i.e. the position and width of the resonance states. The cross sections and the corresponding Maxwellian rate coefficients are computed using a method based on the Multichannel Quantum Defect Theory. The main result of the paper is the very low dissociative recombination rate found at temperatures below 1000K. This is in agreement with the previous upper limit measurement in merged beams and offers a realistic explanation to the presence of ArH+ in exotic interstellar conditions.

Modelling the ArH+ emission from the Crab nebula

Abstract We have performed combined photoionization and photodissociation region (PDR) modelling of a Crab nebula filament subjected to the synchrotron radiation from the central pulsar wind nebula, and to a high flux of charged particles; a greatly enhanced cosmic-ray ionization rate over the standard interstellar value, ζ0, is required to account for the lack of detected [C i] emission in published Herschel SPIRE FTS observations of the Crab nebula. The observed line surface brightness ratios of the OH+ and ArH+ transitions seen in the SPIRE FTS frequency range can only be explained with both a high cosmic-ray ionization rate and a reduced ArH+ dissociative recombination rate compared to that used by previous authors, although consistent with experimental upper limits. We find that the ArH+/OH+ line strengths and the observed H2 vibration–rotation emission can be reproduced by model filaments with nH = 2 × 104 cm−3, ζ = 107ζ0 and visual extinctions within the range found for dusty globules in the Crab nebula, although far-infrared emission from [O i] and [C ii] is higher than the observational constraints. Models with nH = 1900 cm−3 underpredict the H2 surface brightness, but agree with the ArH+ and OH+ surface brightnesses and predict [O i] and [C ii] line ratios consistent with observations. These models predict HeH+ rotational emission above detection thresholds, but consideration of the formation time-scale suggests that the abundance of this molecule in the Crab nebula should be lower than the equilibrium values obtained in our analysis.

Dayside ionosphere of Titan: Impact on calculated plasma densities due to variations in the model parameters

A one dimensional photochemical model for the dayside ionosphere of Titan has been developed for calculating the density profiles of ions and electrons under steady state photochemical equilibrium condition. We concentrated on the T40 flyby of Cassini orbiter and used the in-situ measurements from instruments onboard Cassini as input to the model. An energy deposition model is employed for calculating the attenuated photon flux and photoelectron flux at different altitudes in Titan’s ionosphere. We used the Analytical Yield Spectrum approach for calculating the photoelectron fluxes. Volume production rates of major primary ions, like, N2+, N+, CH4+, CH3+, etc due to photon and photoelectron impact are calculated and used as input to the model. The modeled profiles are compared with the Cassini Ion Neutral Mass Spectrometer (INMS) and Langmuir Probe (LP) measurements. The calculated electron density is higher than the observation by a factor of 2 to 3 around the peak. We studied the impact of different model parameters, viz. photoelectron flux, ion production rates, electron temperature, dissociative recombination rate coefficients, neutral densities of minor species, and solar flux on the calculated electron density to understand the possible reasons for this discrepancy. Recent studies have shown that there is an overestimation in the modeled photoelectron flux and N2+ ion production rates which may contribute towards this disagreement. But decreasing the photoelectron flux (by a factor of 3) and N2+ ion production rate (by a factor of 2) decreases the electron density only by 10 to 20%. Reduction in the measured electron temperature by a factor of 5 provides a good agreement between the modeled and observed electron density. The change in HCN and NH3 densities affects the calculated densities of the major ions (HCNH+, C2H5+, and CH5+); however the overall impact on electron density is not appreciable ( < 20%). Even though increasing the dissociative recombination rate coefficients of the ions C2H5+ and CH5+ by a factor of 10 reduces the difference between modeled and observed densities of the major ions, the modeled electron density is still higher than the observation by ∼ 60% at the peak. We suggest that there might be some unidentified chemical reactions that may account for the additional loss of plasma in Titan’s ionosphere.

Inelastic low-energy collisions of electrons with HeH+: Rovibrational excitation and dissociative recombination.

Inelastic low-energy (0-1 eV) collisions of electrons with HeH+ cations are treated theoretically, with a focus on the rovibrational excitation and dissociative recombination (DR) channels. In an application of ab initio multichannel quantum defect theory, the description of both processes is based on the Born-Oppenheimer quantum defects. The quantum defects were determined using the R-matrix approach in two different frames of reference: the center-of-charge and the center-of-mass frames. The results obtained in the two reference systems, after implementing the Fano-Jungen style rovibrational frame-transformation technique, show differences in the rate of convergence for these two different frames of reference. We find good agreement with the available theoretically predicted rotationally inelastic thermal rate coefficients. Our computed DR rate also agrees well with the available experimental results. Moreover, several computational experiments shed light on the role of rotational and vibrational excitations in the indirect DR mechanism that governs the low energy HeH+ dissociation process. While the rotational excitation is several orders of magnitude more probable process at the studied collision energies, the closed-channel resonances described by the high-n, rotationally excited neutral molecules of HeH contribute very little to the dissociation probability. But the situation is very different for resonances defined by the high-n, vibrationally excited HeH molecules, which are found to dissociate with approximately 90% probability.

Modeling nightglow in atomic oxygen red and green lines under moderate disturbed geomagnetic conditions at midlatitudes

We present results of a study of mid-latitude auroras. The study is based on optical measurements and theoretical modeling. The modeling shows that precipitation can indirectly generate airglow in red and green lines of atomic oxygen by increasing rates of ion formation and heating of thermal electrons. This causes an increase in the rate of dissociative recombination and thermal-electron-collision excitation of the 1D and 1S levels.

PFISR observation of intense ion upflow fluxes associated with an SED during the 1 June 2013 geomagnetic storm

AbstractThe Earth's ionosphere plays an important role in supplying plasma into the magnetosphere through ion upflow/outflow, particularly during periods of strong solar wind driving. An intense ion upflow flux event during the 1 June 2013 storm has been studied using observations from multiple instruments. When the open‐closed field line boundary (OCB) moved into the Poker Flat incoherent scatter radar (PFISR) field of view, divergent ion fluxes were observed by PFISR with intense upflow fluxes reaching ~1.9 × 1014 m−2 s−1 at ~600 km altitude. Both ion and electron temperatures increased significantly within the ion upflow, and thus, this event has been classified as a type 2 upflow. We discuss factors contributing to the high electron density and intense ion upflow fluxes, including plasma temperature effect and preconditioning by storm‐enhanced density (SED). Our analysis shows that the significantly enhanced electron temperature due to soft electron precipitation in the cusp can reduce the dissociative recombination rate of molecular ions above ~400 km and contributed to the density increase. In addition, this intense ion upflow flux event is preconditioned by the lifted F region ionosphere due to northwestward convection flows in the SED plume. During this event, the OCB and cusp were detected by DMSP between 15 and 16 magnetic local times, unusually duskward. Results from a global magnetohydrodynamics simulation using the Space Weather Modeling Framework have been used to provide a global context for this event. This case study provides a more comprehensive mechanism for the generation of intense ion upflow fluxes observed in association with SEDs.

Dissociative recombination of HCl+, H2Cl+, DCl+, and D2Cl+ in a flowing afterglow.

Dissociative recombination of electrons with HCl+, H2Cl+, DCl+, and D2Cl+ has been measured under thermal conditions at 300, 400, and 500 K using a flowing afterglow-Langmuir probe apparatus. Measurements for HCl+ and DCl+ employed the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, while those for H2Cl+ and D2Cl+ employed both VENDAMS and the more traditional technique of monitoring electron density as a function of reaction time. At 300 K, HCl+ and H2Cl+ recombine with kDR = 7.7±2.14.5 × 10-8 cm3 s-1 and 2.6 ± 0.8 × 10-7 cm3 s-1, respectively, whereas D2Cl+ is roughly half as fast as H2Cl+ with kDR = 1.1 ± 0.3 × 10-7 cm3 s-1 (2σ confidence intervals). DCl+ recombines with a rate coefficient below the approximate detection limit of the method (≲5 × 10-8 cm3 s-1) at all temperatures. Relatively slow dissociative recombination rates have been speculated to be responsible for the large HCl+ and H2Cl+ abundances in interstellar clouds compared to current astrochemical models, but our results imply that the discrepancy must originate elsewhere.

Моделирование ночных свечений красной и зеленой линий атомарного кислорода для умеренно-возмущенных геомагнитных условий на средних широтах

We present results of a study of mid-latitude auroras. The study is based on optical measurements and theoretical modeling. The modeling shows that precipitation can indirectly generate airglow in red and green lines of atomic oxygen by increasing rates of ion formation and heating of thermal electrons. This causes an increase in the rate of dissociative recombination and thermal-electron-collision excitation of the 1D and 1S levels.

Electron energetics in the Martian dayside ionosphere: Model comparisons with MAVEN data

AbstractThis paper presents a study of the energetics of the dayside ionosphere of Mars using models and data from several instruments on board the Mars Atmosphere and Volatile EvolutioN spacecraft. In particular, calculated photoelectron fluxes are compared with suprathermal electron fluxes measured by the Solar Wind Electron Analyzer, and calculated electron temperatures are compared with temperatures measured by the Langmuir Probe and Waves experiment. The major heat source for the thermal electrons is Coulomb heating from the suprathermal electron population, and cooling due to collisional rotational and vibrational CO2 dominates the energy loss. The models used in this study were largely able to reproduce the observed high topside ionosphere electron temperatures (e.g., 3000 K at 300 km altitude) without using a topside heat flux when magnetic field topologies consistent with the measured magnetic field were adopted. Magnetic topology affects both suprathermal electron transport and thermal electron heat conduction. The effects of using two different solar irradiance models were also investigated. In particular, photoelectron fluxes and electron temperatures found using the Heliospheric Environment Solar Spectrum Radiation irradiance were higher than those with the Flare Irradiance Spectrum Model‐Mars. The electron temperature is shown to affect the O2+ dissociative recombination rate coefficient, which in turn affects photochemical escape of oxygen from Mars.

DETECTION OF HF TOWARD PKS 1830–211, SEARCH FOR INTERSTELLAR H2F+, AND LABORATORY STUDY OF H2F+ AND H2Cl+ DISSOCIATIVE RECOMBINATION

ABSTRACT We report extragalactic observations of two fluorine-bearing species, hydrogen fluoride (HF) and fluoronium (H2F+), in the z = 0.89 absorber in front of the lensed blazar PKS 1830−211 with the Atacama Large Millimeter/submillimeter Array. HF was detected toward both southwest and northeast images of the blazar, with column densities &gt;3.4 × 1014 cm−2 and 0.18 × 1014 cm−2, respectively. H2F+ was not detected, down to an upper limit (3σ) of 8.8 × 1011 cm−2 and an abundance ratio of [H2F+]/[HF] 1/386. We also searched for H2F+ toward the Galactic sources NGC 6334 I and W51C, and toward Galactic center clouds with the Herschel HIFI spectrometer.6 The upper limit on the column density was derived to be 2.5 × 1011 cm−2 in NGC 6334 I, which is 1/68 of that for H2Cl+. In constrast, the ortho transition of H2Cl+ is detected toward PKS 1830–211. To understand the small abundance of interstellar H2F+, we carried out laboratory experiments to determine the rate constants for the ion–electron recombination reaction by infrared time-resolved spectroscopy. The constants determined are k e (209 K) = cm3 s−1 and cm3 s−1 for H2F+ and H2Cl+, respectively. The difference in the dissociative recombination rates between H2F+ and H2Cl+ by a factor ∼2 and the cosmic abundance ratio [F]/[Cl] ≈ 1/6 are not enough to explain the much smaller abundance of H2F+. The difference in the formation mechanism of H2F+ and H2Cl+ in interstellar space would be a major factor in the small abundance of H2F+.