Hydrogen isotopic substitution of solid methylamine through atomic surface reactions at low temperatures: A potential contribution to the D/H ratio of methylamine in molecular clouds

We experimentally studied hydrogen (H)–deuterium (D) substitution reactions of solid methylamine (CH₃NH₂) under astrophysically relevant conditions. We also calculated the potential energy surface for the H–D substitution reactions of methylamine isotopologues using quantum chemical methods. Despite the relatively large energy barrier of more than 18 kJ mol^?1, CH₃NH₂ reacted with D atoms to yield deuterated methylamines at 10 K, suggesting that the H–D substitution reaction proceeds through quantum tunneling. Deuterated methylamines reacted with H atoms as well. On the basis of present results, we propose that methylamine has potential for D enrichment through atomic surface reactions on interstellar grains at very low temperatures in molecular clouds. D enrichment would occur in particular in the methyl group of methylamine.     

Deuterium fractionation in the presolar nebula: Kinetic limitations on surface catalysis

Models assuming low temperature equilibrium fractionation have previously been employed to explain the range of D/H values observed in the solar system and to make predictions of deuterium enhancement in the outer planets. While the reaction rates of the homogeneous partitioning reactions are prohibitively low at nebular temperatures, it has been suggested that catalysis on grains could shorten equilibrium times sufficiently. This idea is quantitatively tested here. We find that under highly idealized conditions—the full cosmic abundance of nickel available for catalysis in pure 5-μm grains—the equilibrium time constant becomes greater than the lifetime of the nebula at temperatures lower than 560°K. Even this firm lower limit is not cold enough to allow strong fractionation. Speculations are offered on alternative explanations for the distribution of hydrogen isotopes in the solar system.     

The possibility of nitrogen isotopic fractionation in interstellar clouds

The possibility of nitrogen isotopic fractionation owing to ion–molecule exchange reactions involving the most abundant N-containing species in dense interstellar clouds has been explored. We find that exchange reactions between N atoms and N-containing ions have most influence on the fractionation, although the extent of fractionation is too small to be readily detectable.     

Ab initio characterization of MgCCH, MgCCH+, and MgC2 and pathways to their formation in the interstellar medium

A study of Mg-bearing compounds has been performed in order to determine molecular properties which are critical for planning new astronomical searches and laboratory studies. The primary focus of the work is on MgCCH, MgCCH+, and the isomers of MgC2. Only MgCCH has been identified in laboratory studies. Additional calculations have been carried out on MgH, MgNC, MgCN, and their cations in an effort to evaluate pathways to the formation of MgCCH and MgCCH+ in the interstellar medium (ISM) or in circumstellar envelopes. Correlated ab initio methods and correlation-consistent basis sets have been employed. Properties including structures, rotational constants, dipole moments, and harmonic frequencies are reported. A transition state between linear MgCC and cyclic MgC2 has been characterized and was found to yield a minimal barrier (approximately 0.5 kcal mole-1), indicating easy interconversion to the cyclic form. Direct reactions in the ISM between Mg or Mg+ and HCCH are precluded by energetic considerations, but a number of ion-molecule or neutral-neutral exchange reactions between CCH and various Mg-containing species offer plausible pathways to MgCCH or MgCCH+. Weakly bound MgH may react with CCH to form MgCCH, but MgH has not been detected. Both MgNC and MgCN have been observed, but reactions with CCH are slightly endothermic by 1-3 kcal mole-1. Although MgH+, MgNC+, and MgCN+ have not been detected, their reactions with CCH to form MgCCH+ are all exothermic. With only a small barrier separating linear MgCC and cyclic MgC2, the dissociative recombination of MgCCH+ with an electron is expected to yield cyclic MgC2 and regenerate Mg and CCH. New astronomical searches for MgCCH, MgCCH+, cyclic MgC2, MgNC+, and MgCN+ will provide further insight into organo-magnesium astrochemistry.     

Fractionation of hydrogen and deuterium on Venus due to collisional ejection

The fractionation factor f is important for interpreting the current escape fluxes of H and D on Venus and how the D/H ratio has evolved. The escape flux is currently governed by the two processes of charge exchange and collisional ejection by fast oxygen atoms. Using a best-fit parameterized equation for the O-H scattering angle phase function, more accurate branching ratios for the oxygen ion dissociation and including the effects of the initial energy and momentum of the ions and electrons, as well as for the hydrogen and deuterium gas, we have reanalyzed the collisional ejection process. Our analysis produces improved values for the efficiency of H and D escape as a function of the ionospheric temperature. From our results we propose the reduction of the hydrogen flux for collisional ejection from 8 to 3.5 x 10(6) cm-2 s-1. Assuming that collisions leading to escape occur mostly in the region between 200 and 400 km, the revised D/H fractionation factor due to collisional ejection is 0.47, where previously the process had been considered completely discriminating against deuterium escape (or f approximately 0.) The resulting deuterium flux is 3.1 x 10(4) cm-2 s-1, roughly 6 times the flux due to charge exchange, making collisional ejection the dominant escape mechanism for deuterium on Venus.     

Deuterium enrichment of the interstellar medium

Despite the low elemental abundance of atomic deuterium in the interstellar medium (ISM), observational evidence suggests that several species, both in the gas phase and in ices, could be heavily fractionated. We explore various aspects of deuterium enrichment by constructing a chemical evolution model in both gaseous and granular phases. Depending on various physical parameters, gases and grains are allowed to interact with each other through the exchange of their chemical species. It is known that HCO⁺ and N₂H⁺ are two abundant gas phase ions in the ISM and, their deuterium fractionation is generally used to predict the degree of ionization in the various regions of a molecular cloud. For a more accurate estimation, we consider the density profile of a collapsing cloud. The radial distributions of important interstellar molecules, along with their deuterated isotopomers, are presented. Quantum chemical simulations are computed to study the effects of isotopic substitution on the spectral properties of these interstellar species. We calculate the vibrational (harmonic) frequencies of the most important deuterated species (neutral and ions). The rotational and distortional constants of these molecules are also computed in order to predict the rotational transitions of these species. We compare vibrational (harmonic) and rotational transitions as computed by us with existing experimental and theoretical results. It is hope that our results will assist observers in detecting several hitherto unobserved deuterated species.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Deuterated water: partition functions and equilibrium constants

HDO and D₂O are thought to be present in significant quantities in the coldest regions of the Universe. Partition functions are calculated for these species and used to calculate temperature dependent equilibrium constants for the most important fractionation reactions involving water. HDO may also be a key indicator of the absence of deuterium burning in very low mass stars. The HDO partition function calculation is extended to high  ( T ≤ 6000 K)  temperatures for this purpose.     

The diurnal variation of atomic hydrogen

This note critically examines the relative importance of several effects which influence the diurnal variation of atomic hydrogen abundance near the critical level.It is pointed out that the neglect of exospheric hydrogen in a recent theoretical treatment causes an overestimation of the diurnal variation at high exospheric temperatures, and an underestimation at low exospheric temperatures. The fluxes due to lateral flow are large compared to other fluxes only to the extent that the actual diurnal variation is very different from the diurnal variation corresponding to zero net lateral flow, which does not seem to be the case in the real atmosphere. Two effects which are probably important are charge exchange reactions with thermal oxygen ions, resulting in a diurnal exchange with the plasmasphere; and charge exchange reactions with high velocity protons, resulting in enhanced escape and diurnal variation.     

A multi‐step model for the origin of E3 (enstatite) chondrites

Abstract— It appears that the mineralogy and chemical properties of type 3 enstatite chondrites could have been established by fractionation processes (removal of a refractory component, and depletion of water) in the solar nebula, and by equilibration with nebular gas at low‐to‐intermediate temperatures (approximately 700–950 K). We describe a model for the origin of type 3 enstatite chondrites that for the first time can simultaneously account for the mineral abundances, bulk‐chemistry, and phase compositions of these chondrites by the operation of plausible processes in the solar nebula. This model, which assumes a representative nebular gas pressure of 10^?5 bar, entails three steps: (1) initial removal of 56% of the equilibrium condensed phases in a system of solar composition at 1270 K; (2) an average loss of 80–85% water vapor in the remaining gas; and (3) two different closure temperatures for the condensed phases. The first step involves a “refractory element fractionation” and is needed to account for the overall major element composition of enstatite chondrites, assuming an initial system with a solar composition. The second step, water‐vapor depletion, is needed to stabilize Si‐bearing metal, oldhamite, and niningerite, which are characteristic minerals of the enstatite chondrites. Variations in closure temperatures are suggested by the way in which the bulk chemistry and mineral assemblages of predicted condensates change with temperature, and how these parameters correlate with the observations of enstatite chondrites. In general, most phases in type 3 enstatite chondrites appear to have ceased equilibrating with nebular gas at approximately 900–950 K, except for Fe‐metal, which continued to partially react with nebular gas to temperatures as low as ～700 K.     

Helium escape from the Earth''s atmosphere: The charge exchange mechanism revisited

We have studied the escape of neutral helium from the terrestrial atmosphere through exothermic charge exchange reactions between He⁺ ions and the major atmospheric constituents N₂, O₂, and O. Elastic collisions with the neutral background particles were treated quantitatively using a recently developed kinetic theory approach. An interhemispheric plasma transport model was employed to provide a global distribution of He⁺ ions as a function of altitude, latitude and local solar time and for different levels of solar ionization. Combining these ion densities with neutral densities from an MSIS model and best estimates for the reaction rate coefficients of the charge exchange reactions, we computed the global distribution of the neutral He escape flux. The escape rates show large diurnal and latitudinal variations, while the global average does not vary by more than a factor of three over a solar cycle. We find that this escape mechanism is potentially important for the overall balance of helium in the Earth's atmosphere. However, more accurate values for the reaction rate coefficients of the charge exchange reactions are required to make a definitive assessment of its importance.     

Population of excited rotational levels of HD and CO in interstellar clouds

Populations of the rotational levels of vibrational and electronic ground state of interstellar HD and CO have been calculated. Ultraviolet pumping and molecular formation have been found to be very important in the case of HD but not so in CO, the population distribution of which is mainly governed either by 3 K or by collisional excitation. The population inversion has been found to occur in HD but not in CO, the excitation temperatures of which pass through maximum for large ultraviolet flux. The population inversion at large density does not occur in HD, probably due to neglect of multipole collision. The observation of HD and CO in the excited states may be possible for suitable values of density and ultraviolet flux.On leave from Tata Institute of Fundamental Research, Bombay, India.     

Ion-molecule calculation of the abundance ratio of CCD to CCH in dense interstellar clouds

Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2+ (HD) = C2HD+ (H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.01-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.     

Theoretical predictions of deuterium abundances in the Jovian planets

Using current concepts for the origin of the Jovian planets and current constraints on their interior structure, we argue that the presence of large amounts of “ice” (H₂O, CH₄, and NH₃) in Uranus and Neptune indicates temperatures low enough to condense these species at the time Uranus and Neptune formed. Yet such low temperatures imply orders-of-magnetude fractionation effects for deuterium into the “ice” component if isotopic equilibration can occur. Our models thus imply that Uranus and Neptune should have a D/H ratio at least four times primordial, contrary to observation for Uranus. We find that the Jovian and Saturnian D/H should be close to primordial regardless of formation scenario. The Uranus anomaly could indicate that there was a strong initial radial gradient in D/H in the primordial solar nebula, or that Uranus is so inactive that no significant mixing of its interior has occurred over the age of the solar system. Observation of Neptune's atmospheric D/H may help to resolve the problem.     

Charged-particle induced thermonuclear reaction rates of 3He(3He,2p)4He, 3He(4He,γ)7Be and 7Be(p,γ)8B by using the exact tunneling probability

The astrophysical S-factor of the experimental cross section data of the main reactions in the proton–proton chain, i.e. ³He(³He,2p)⁴He, ³He(⁴He,γ)⁷Be and ⁷Be(p,γ)⁸B, are reanalyzed by using the exact tunneling probability in nuclear reactions. Our goal is to test this treatment in finding the reaction rate per pair for non-resonant reactions. At low temperatures, the exact treatment is identical to the standard formalism but diverges at higher temperatures.     

Transport,charge exchange and loss of energetic heavy ions in the earth's radiation belts: Applicability and limitations of theory

Ions in the trapping region of the earth's magnetosphere are subject to physical and chemical interactions which control their absolute and relative abundances. Charge exchange reactions act to establish a distribution of ionic states that is largely determined by the chemical properties of the individual species. Convection (“drift”) mechanisms and cross-L diffusion cause ions to be distributed over the entire trapping region with flux intensities determined by the nature and strength of the ion source, transport and loss mechanisms which in general are dependent on energy, mass and charge. Current theories describe ion transport through path tracing for individual particles or by radial diffusion for a population as a whole based on stochastic analysis; a comprehensive treatment of the combined convection and diffusion for trapped and non-trapped ions is yet to be developed. Even in studies where diffusion is the sole transport mechanism considered, only equatorially mirroring particles ($\text{α}{}_0\text{=}\text{π}\text{2}$) have been theoretically treated. There are clearly both upper and lower bounds on the ion energy beyond which diffusion theory ceases to be valid: at high energies where the ion gyroradius becomes too large for the adiabatic approximations to be valid and at low energies where convective drift is a dominant process. In spite of the known shortcomings of the diffusion theory and associated modeling, intriguing theoretical predictions of the relative ionic composition of the radiation belts have been made and some of them are now confirmed by direct observation. Among them is the predicted importance of ions heavier than protons at ring current energies of tens of keV which follows from the charge exchange chemistry.     

Laboratory experiments bearing on the origin and evolution of olivine‐rich chondrules

Abstract– Evaporation rates of K₂O, Na₂O, and FeO from chondrule‐like liquids and the associated potassium isotopic fractionation of the evaporation residues were measured to help understand the processes and conditions that affected the chemical and isotopic compositions of olivine‐rich type IA and type IIA chondrules from Semarkona. Both types of chondrules show evidence of having been significantly or totally molten. However, these chondrules do not have large or systematic potassium isotopic fractionation of the sort found in the laboratory evaporation experiments. The experimental results reported here provide new data regarding the evaporation kinetics of sodium and potassium from a chondrule‐like melt and the potassium isotopic fractionation of evaporation residues run under various conditions ranging from high vacuum to pressures of one bar of H₂+CO₂, or H₂, or helium. The lack of systematic isotopic fractionation of potassium in the type IIA and type IA chondrules compared with what is found in the vacuum and one‐bar evaporation residues is interpreted as indicating that they evolved in a partially closed system where the residence time of the surrounding gas was sufficiently long for it to have become saturated in the evaporating species and for isotopic equilibration between the gas and the melt. A diffusion couple experiment juxtaposing chondrule‐like melts with different potassium concentrations showed that the diffusivity of potassium is sufficiently fast at liquidus temperatures (D_K > 2 × 10^?4cm² s^?1 at 1650 °C) that diffusion‐limited evaporation cannot explain why, despite their having been molten, the type IIA and type IA chondrules show no systematic potassium isotopic fractionation.     

The primary liquid condensation model and the origin of barred olivine chondrules

Barred olivine (BO) chondrules are some of the most striking objects in chondrites. Their ubiquitous presence and peculiar texture caught the attention of researchers and, as a consequence, considerable effort has been expensed on unraveling their origin(s). Here we report on a detailed study of two types of chondrules: the Classic and the Multiple-Plate Type of BO chondrules from the Essebi (CM2), Bishunpur (LL3.1), Acfer 214 (CH3) and DAG 055 (C3-UNGR) chondrites, and discuss the petrographic and chemical data of their major mineral phases and glasses. Glasses occur as mesostasis or as glass inclusions, the latter either enclosed inside the olivine bars (plates) or still connected to the mesostasis. The chemical composition of all glasses, characterized by being Si-Al-Ca-rich and free of alkali elements, is similar to those of the constituents (the building blocks, such as chondrules, aggregates, inclusions, mineral fragments, etc.) of CR and CV3 chondrites. They all have high trace element contents (∼10×CI) with unfractionated CI-normalized abundances of refractory trace elements and depletions in moderately volatile and volatile elements with respect to the refractory trace elements. The presence of alkali elements (Na + K + Rb) is coupled with a low Ca content and is only observed in those glasses that have behaved as open systems. This result supports the previous finding that Ca was replaced by alkalis (e.g., Na-Ca exchange), presumably through a vapor-solid reaction. The glasses apparently are the quenched liquid from which the olivine plates crystallized. However, they do not show any chemical fractionation that could have resulted from the crystallization of the olivines, but rather have a constant chemical compositions throughout the formation of the chondrule. In a previous contribution we were able to demonstrate the role of these liquids in supporting crystal growth directly from the vapor. Here we extend application of the primary liquid condensation model to formulate a new model for the origin of BO chondrules. The primary liquid condensation model is based on the ability of dust-enriched solar-nebula gas to directly condense into a liquid, provided the gas/dust ratio is sufficiently low. Thus, we propose that chondrules can be formed by condensation of a liquid droplet directly from the solar nebula. The extensive variability in chemical composition of BO chondrules, which ranges from alkali-poor to alkali-rich, can be explained by elemental exchange reactions with the cooling nebula. We calculate the chemical composition of the initial liquid droplet from which BO chondrules could have formed and speculate about the physical and chemical conditions that prevail in the specific regions of the solar nebula that can promote creation of these objects.     

The lack of potassium‐isotopic fractionation in Bishunpur chondrules

Abstract— In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K‐isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ⁴¹K compositions that were normal within error (typically ±3%, 2s?). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large ⁴¹K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ⁴¹K is produced by ～12% loss of K. The range of L‐chondrite‐normalized K/Al ratios (a measure of the K‐elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L‐chondrite‐like K abundances and the K loss occurred via Rayleigh fractionation, the most K‐depleted chondrules would have had compositions of up to δ⁴¹K ? 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K‐isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K‐isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim‐matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have alkali abundances that are much lower than the mesostases of the host chondrules, which suggests that they at least remained closed since formation. If it is correct that some or all melt inclusions remained closed since formation, the absence of K‐isotopic fractionation in them requires that the K‐isotopic exchange took place during chondrule formation, which would probably require gas‐chondrule exchange. Potassium evaporated from fine‐grained dust and chondrules during chondrule formation may have produced sufficient K‐vapor pressure for gas‐chondrule isotopic exchange to be complete on the timescales of chondrule formation. Alternatively, our understanding of chondrule formation conditions based on synthesis experiments needs some reevaluation.     

Solar system X‐rays from charge exchange processes

While X‐ray astronomy began in 1962 and has made fast progress since then in expanding our knowledge about where in the Universe X‐rays are generated by which processes, it took one generation before the importance of a fundamentally different process was recognized. This happened in our immediate neighborhood, when in 1996 comets were discovered as a new class of X‐ray sources, directing our attention to charge exchange reactions. Charge exchange is fundamentally different from other processes which lead to the generation of X‐rays, because the X‐rays are not produced by hot electrons, but by ions picking up electrons from cold gas. Thus it opens up a new window, making it possible to detect cool gas in X‐rays (like in comets), while all the other processes require extremely high temperatures or otherwise extreme conditions. After having been overlooked for a long time, the astrophysical importance of charge exchange for the generation of X‐rays is now receiving increased general attention. In our solar system, charge exchange induced X‐rays have now been established to originate in comets, in all the planets from Venus to Jupiter, and even in the heliosphere itself. In addition to that, evidence for this X‐ray emission mechanism has been found at various locations across the Universe. Here we summarize the current knowledge about solar system X‐rays resulting from charge exchange processes (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)