Recommended Thermal Rate Coefficients for the C + H3+_3^+ Reaction and Some Astrochemical Implications

We have incorporated our experimentally derived thermal rate coefficients for C + H$_3^+$ forming CH$^+$ and CH$_2^+$ into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and use instead a more versatile fitting formula. At a temperature of 10 K and a density of 10$^4$ cm$^{-3}$, we find no significant differences in the predicted chemical abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. Additionally, we find that the relatively small error on our thermal rate coefficients, $\sim15\%$, significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.Comment: 19 pages, 5 figures. Accepted for publication in Ap

Merged-beams Reaction Studies of O + H_3^+

We have measured the reaction of O + H3+ forming OH+ and H2O+. This is one of the key gas-phase astrochemical processes initiating the formation of water molecules in dense molecular clouds. For this work, we have used a novel merged fast-beams apparatus which overlaps a beam of H3+ onto a beam of ground-term neutral O. Here, we present cross section data for forming OH+ and H2O+ at relative energies from \approx 3.5 meV to \approx 15.5 and 0.13 eV, respectively. Measurements were performed for statistically populated O(3PJ) in the ground term reacting with hot H3+ (with an internal temperature of \approx 2500-3000 K). From these data, we have derived rate coefficients for translational temperatures from \approx 25 K to \approx 10^5 and 10^3 K, respectively. Using state-of-the-art theoretical methods as a guide, we have converted these results to a thermal rate coefficient for forming either OH+ or H2O+, thereby accounting for the temperature dependence of the O fine-structure levels. Our results are in good agreement with two independent flowing afterglow measurements at a temperature of \approx 300 K, and with a corresponding level of H3+ internal excitation. This good agreement strongly suggests that the internal excitation of the H3+ does not play a significant role in this reaction. The Langevin rate coefficient is in reasonable agreement with the experimental results at 10 K but a factor of \approx 2 larger at 300 K. The two published classical trajectory studies using quantum mechanical potential energy surfaces lie a factor of \approx 1.5 above our experimental results over this 10-300 K range.Comment: 43 pages, 11 figures. Submitted to the Astrophysical Journa

Ro-vibrational analysis of the XUV photodissociation of HeH+^+ ions

We investigate the dynamics of the photodissociation of the hydrohelium cation HeH$^+$ by XUV radiation with the aim to establish a detailed comparison with a recent experimental work carried out at the FLASH free electron laser using both vibrationally hot and cold ions. As shown in previous theoretical works, the comparison is hindered by the fact that the experimental ro-vibrational distribution of the ions is unknown. We determine this distribution using a dissociative charge transfer set-up and the same source conditions as in the FLASH experiment. Using a non-adiabatic time-dependent wave packet method, we calculate the partial photodissociation cross sections for the $n=1-3$ coupled electronic states of HeH$^+$. We find a good agreement with the experiment for the total cross section into the He + H$^+$ dissociative channel. By performing an adiabatic calculation involving the $n=4$ states, we then show that the experimental observation of the importance of the electronic states with $n>3$ cannot be well explained theoretically, especially for cold ($v=0$) ions. We also calculate the relative contributions to the cross section of the $\Sigma$ and $\Pi$ states. The agreement with the experiment is excellent for the He$^+$ + H channel, but only qualitative for the He + H$^+$ channel. We discuss the factors that could explain the remaining discrepancies between theory and experiment.Comment: 10 pages, 8 figure

Absolute energy-resolved measurements of the H-+H→H2+e- associative detachment reaction using a merged-beam apparatus

Using a merged-beam configuration, we have performed absolute measurements for the associative detachment reaction H-+H→H2+e-. Our energy-resolved measurements for this process remove a long-standing discrepancy between theory and experiment for this fundamental reaction. In particular, we find excellent agreement with theoretical results which previously seemed to be ruled out by earlier experiments performed using a flowing afterglow technique

A novel merged beam apparatus to study the cosmic origins of organic chemistry

Reactions of atomic carbon with molecular ions play a critical role for gas phase molecular formation in interstellar clouds. These interactions are the first links in the chain of chemical reactions leading to the synthesis of complex organic species. Much of our knowledge of this process is through spectroscopic observations and theoretical models. However, our understanding of this chemistry is constrained by uncertainties in the underlying reaction rate coefficients. Data from quantum calculations are limited to reactions involving three or fewer atoms. Meanwhile, previous experimental studies have been hampered by the difficulty in generating a sufficiently intense and well characterized neutral carbon beam. To address these issues and to study these reactions experimentally, we are building a novel laboratory device which does not suffer from such limitation

Evidence for two-electron processes in the mutual neutralization of O- with O+ and N+ at Subthermal Collision Energies

We have measured total absolute cross sections for the Mutual Neutralization (MN) of O- with O+/N+. A fine resolution (of about 50 meV) in the kinetic energy spectra of the product neutral atoms allows unique identification of the atomic states participating in the mutual neutralization process. Cross sections and branching ratios have also been calculated down to 1 meV center-of-mass collision energy for these two systems with a multi-channel Landau-Zener model and an asymptotic method for the ionic-covalent coupling matrix elements. The importance of two-electron processes in one-electron transfer is demonstrated by the dominant contribution of a core-excited configuration of the nitrogen atom in N+ + O- collisions. This effect is partially accounted for by introducing configuration mixing in the evaluation of coupling matrix elements.Comment: 5 pages, 4 figure

Generation of neutral atomic beams utilizing photodetachment by high power diode laser stacks

We demonstrate the use of high power diode laser stacks to photodetach fast hydrogen and carbon anions and produce ground term neutral atomic beams. We achieve photodetachment efficiencies of $\sim$7.4\% for H$^-$ at a beam energy of 10\,keV and $\sim$3.7\% for C$^-$ at 28\,keV. The diode laser systems used here operate at 975\,nm and 808\,nm, respectively, and provide high continuous power levels of up to 2\,kW, without the need of additional enhancements like optical cavities. The alignment of the beams is straightforward and operation at constant power levels is very stable, while maintenance is minimal. We present a dedicated photodetachment setup that is suitable to efficiently neutralize the majority of stable negative ions in the periodic table

Associative detachment of H− + H → H2 + e−

Using a merged-beams apparatus, we have measured the associative detachment (AD) reaction of H−+H→H2+e− for relative collision energies up to Er≤4.83 eV. These data extend above the 1-eV limit of our earlier results. We have also updated our previous theoretical work to account for AD via the repulsive 2Σg+ H2− potential energy surface and for the effects at Er≥0.76 eV on the experimental results due to the formation of long-lived H2 resonances lying above the H+H separated atoms limit. Merging both experimental data sets, our results are in good agreement with our new theoretical calculations and confirm the prediction that this reaction essentially turns off for Er≳2 eV. Similar behavior has been predicted for the formation of protonium from collisions of antiprotons and hydrogen atoms

Molecular Hydrogen Formation in the Early Universe: New Implications From Laboratory Measurements

We have performed the first energy-resolved measurement of the associative detachment (AD) reaction H- + H → H2 + e-: This reaction is the dominant formation pathway for H2 during the epoch of first star formation in the early universe. Despite being the most fundamental anion-neutral chemical reaction, experiment and theory have failed to converge in both magnitude and energy dependence. The uncertainty in this rate coefficient severely limits our under- standing of the formation of the first stars and protogalaxies

Molecular Hydrogen Formation in the Early Universe: New Implications From Laboratory Measurements

We have performed the first energy-resolved measurement of the associative detachment (AD) reaction H- + H → H2 + e-: This reaction is the dominant formation pathway for H2 during the epoch of first star formation in the early universe. Despite being the most fundamental anion-neutral chemical reaction, experiment and theory have failed to converge in both magnitude and energy dependence. The uncertainty in this rate coefficient severely limits our under- standing of the formation of the first stars and protogalaxies