Matthew J. Abplanalp

A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules

Significance Since the detection of the methylidyne radical (CH) in the interstellar medium nearly 80 y ago, about 200 molecules ranging from molecular hydrogen to fullerenes have been identified in interstellar and circumstellar environments, but the synthesis of complex organic molecules (COMs)––organics containing several atoms of carbon, hydrogen, nitrogen, and oxygen––has remained elusive to date. Here, we provide compelling evidence via laboratory experiments, computations, and modeling that the synthesis of COMs is driven by a cosmic-ray-triggered nonequilibrium chemistry within interstellar ices at temperatures as low as 10 K. These fundamental reaction mechanisms are of major significance to facilitate an understanding of the origin and evolution of the molecular universe. Complex organic molecules such as sugars and amides are ubiquitous in star- and planet-forming regions, but their formation mechanisms have remained largely elusive until now. Here we show in a combined experimental, computational, and astrochemical modeling study that interstellar aldehydes and enols like acetaldehyde (CH3CHO) and vinyl alcohol (C2H3OH) act as key tracers of a cosmic-ray-driven nonequilibrium chemistry leading to complex organics even deep within low-temperature interstellar ices at 10 K. Our findings challenge conventional wisdom and define a hitherto poorly characterized reaction class forming complex organic molecules inside interstellar ices before their sublimation in star-forming regions such as SgrB2(N). These processes are of vital importance in initiating a chain of chemical reactions leading eventually to the molecular precursors of biorelevant molecules as planets form in their interstellar nurseries.

PROBING THE CARBON–PHOSPHORUS BOND COUPLING IN LOW-TEMPERATURE PHOSPHINE (PH3)–METHANE (CH4) INTERSTELLAR ICE ANALOGUES

Phosphine, which has now been confirmed around the carbon-rich star IRC+10216, provides the first example of a phosphorus-containing single bond in interstellar or circumstellar media. While four compounds containing both phosphorus and carbon have been discovered, none contain a carbon-phosphorus single bond. Here, we show that this moiety is plausible from the reaction of phosphine with methane in electron-irradiated interstellar ice analogues. Fractional sublimation allows for detection of individual products at distinct temperatures using reflectron time-of-flight mass spectrometry (ReTOF) coupled with vacuum ultraviolet photoionization. This method produced phosphanes and methylphosphanes as large as P8H10 and CH3P8H9, which demonstrates that a phosphorus-carbon bond can readily form and that methylphosphanes sublime at 12-17 K higher temperatures than the non-organic phosphanes. Also, irradiated ices of phosphine with deuterated-methane untangle the reaction pathways through which these methylphosphanes were formed and identified radical recombination to be preferred over carbene/phosphinidene insertion reactions. In addition, these ReTOF results confirm that CH3PH2 and CH6P2 can form via insertion of carbene and phosphinidene and that the methylenediphosphine (PH2CH2PH2) isomer forms in the ices, although methylphosphine (CH3P2H3) is likely the more abundant isomer and that phosphanes and organophosphanes preferentially fragment via the loss of a phosphino group when photoionized. While the formation of methylphosphine is overall endoergic, the intermediates produced by interactions with energetic electrons proceed toward methylphosphine favorably and barrierlessly and provide plausible mechanisms toward hitherto unidentified interstellar compounds.

MECHANISTIC STUDIES ON THE RADIOLYTIC DECOMPOSITION OF PERCHLORATES ON THE MARTIAN SURFACE

Perchlorates—inorganic compounds carrying the perchlorate ion (ClO4 - )—were discovered at the north polar landing site of the Phoenix spacecraft and at the southern equatorial landing site of the Curiosity Rover within the Martian soil at levels of 0.4–0.6 wt%. This study explores in laboratory experiments the temperature-dependent decomposition mechanisms of hydrated perchlorates—namely magnesium perchlorate hexahydrate (Mg(ClO4)2·6H2O) —and provides yields of the oxygen-bearing species formed in these processes at Mars-relevant surface temperatures from 165 to 310 K in the presence of galactic cosmic-ray particles (GCRs). Our experiments reveal that the response of the perchlorates to the energetic electrons is dictated by the destruction of the perchlorate ion (ClO4 - ) and the inherent formation of chlorates (ClO3 - ) plus atomic oxygen (O). Isotopic substitution experiments reveal that the oxygen is released solely from the perchlorate ion and not from the water of hydration (H2O). As the mass spectrometer detects only molecular oxygen (O2) and no atomic oxygen(O), atomic oxygen recombines to molecular oxygen within the perchlorates, with the overall yield of molecular oxygen increasing as the temperature drops from 260 to 160 K. Absolute destruction rates and formation yields of oxygen are provided for the planetary modeling community.

ON THE FORMATION AND ISOMER SPECIFIC DETECTION OF PROPENAL (C2H3CHO) AND CYCLOPROPANONE (c-C3H4O) IN INTERSTELLAR MODEL ICES—A COMBINED FTIR AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDY

The formation routes of two structural isomers—propenal (C2H3CHO) and cyclopropanone (c-C3H4O)—were investigated experimentally by exposing ices of astrophysical interest to energetic electrons at 5.5 K thus mimicking the interaction of ionizing radiation with interstellar ices in cold molecular clouds. The radiationinduced processing of these ices was monitored online and in situ via Fourier Transform Infrared spectroscopy and via temperature programmed desorption exploiting highly sensitive reflectron time-of-flight mass spectrometry coupled with single photon ionization in the post irradiation phase. To selectively probe which isomer(s) is/are formed, the photoionization experiments were conducted with 10.49 and 9.60 eV photons. Our studies provided compelling evidence on the formation of both isomers—propenal (C2H3CHO) and cyclopropanone (c-C3H4O)—in ethylene (C2H4)—carbon monoxide (CO) ices forming propenal and cyclopropanone at a ratio of (4.5± 0.9):1. Based on the extracted reaction pathways, the cyclopropanone molecule can be classified as a tracer of a low temperature non-equilibrium chemistry within interstellar ices involving most likely excited triplet states, whereas propenal can be formed at ultralow temperatures, but also during the annealing phase via non-equilibrium as well as thermal chemistry (radical recombination). Since propenal has been detected in the interstellar medium and our laboratory experiments demonstrate that both isomers originated from identical precursor molecules our study predicts that the hitherto elusive second isomer—cyclopropanone—should also be observable toward those astronomical sources such as Sgr B2(N) in which propenal has been detected.

EFFECT OF PERCHLORATES ON ELECTRON RADIOLYSIS OF GLYCINE WITH APPLICATION TO MARS

This work explores the radiolytic decomposition of glycine (H2NCH2COOH) under simulated Martian conditions in the presence of perchlorates ( ClO4 ), which are abundant oxidizers on the surface of Mars, by energetic electrons at 10, 160, 210, and 260 K, mimicking the radiation exposure of the Martian regolith in the first 5–10 cm depths over about 250 million years. Our experiments present quantitative evidence that the rate constants of the glycine decomposition in the presence of magnesium perchlorate hexahydrate (Mg(ClO4)2 ·6H2O) were a factor of about two higher than that of the pure glycine, suggesting that energetic oxygen atoms (O) released from the ClO4 have a significant effect on the decomposition rates and accelerate them by providing a unique oxidizing environment in the radiolyzed samples. Hence, two decay mechanisms exist: radiolysis by the electrons and oxidation by the O atoms. Within the Mars-relevant temperature range covering 160–260 K, the destruction rates are nearly temperature invariant with rates varying as little as 5%. Further, the formation rates of carbon dioxide (CO2) and carbon monoxide (CO) are both accelerated in the presence of ClO4 by a factor of three to five, supporting our conclusion of an active oxygen-initiated chemistry. In addition, the degradation rates are significantly higher than the formation rates of CO2 and CO. This suggests that, besides the decarboxylation, alternative degradation pathways such as a polymerization of glycine must exist. Finally, besides CO2 and CO, three alternative products were identified tentatively: methylamine (CH3NH2), methane (CH4), and ammonia (NH3).

COMPLEX HYDROCARBON CHEMISTRY IN INTERSTELLAR AND SOLAR SYSTEM ICES REVEALED: A COMBINED INFRARED SPECTROSCOPY AND REFLECTRON TIME-OF-FLIGHT MASS SPECTROMETRY ANALYSIS OF ETHANE (C2H6) AND D6-ETHANE (C2D6) ICES EXPOSED TO IONIZING RADIATION

The irradiation of pure ethane (C2H6/C2D6) ices at 5.5 K, under ultrahigh vacuum conditions was conducted to investigate the formation of complex hydrocarbons via interaction with energetic electrons simulating the secondary electrons produced in the track of galactic cosmic rays. The chemical modifications of the ices were monitored in situ using Fourier transform infrared spectroscopy (FTIR) and during temperature-programmed desorption via mass spectrometry exploiting a quadrupole mass spectrometer with electron impact ionization (EIQMS) as well as a reflectron time-of-flight mass spectrometer coupled to a photoionization source (PI-ReTOFMS). FTIR confirmed previous ethane studies by detecting six molecules: methane (CH4), acetylene (C2H2), ethylene (C2H4), the ethyl radical (C2H5), 1-butene (C4H8), and n-butane (C4H10). However, the TPD phase, along with EI-QMS, and most importantly, PI-ReTOF-MS, revealed the formation of at least 23 hydrocarbons, many for the first time in ethane ice, which can be arranged in four groups with an increasing carbon-to-hydrogen ratio: CnH2n+2 (n = 3, 4, 6, 8, 10), CnH2n (n = 3–10), C H n n 2 2 (n = 3–10), and C H n n 2 4 (n = 4–6). The processing of simple ethane ices is relevant to the hydrocarbon chemistry in the interstellar medium, as ethane has been shown to be a major product of methane, as well as in the outer solar system. These data reveal that the processing of ethane ices can synthesize several key hydrocarbons such as C3H4 and C4H6 isomers, which have been found to synthesize polycyclic aromatic hydrocarbons like indene (C9H8) and naphthalene (C10H8) in the ISM and in hydrocarbon-rich atmospheres of planets and their moons such as Titan.

An Infrared Spectroscopic Study Toward the Formation of Alkylphosphonic Acids and Their Precursors in Extraterrestrial Environments

The only known phosphorus-containing organic compounds of extraterrestrial origin, alkylphosphonic acids, were discovered in the Murchison meteorite and have accelerated the hypothesis that reduced oxidation states of phosphorus were delivered to early Earth and served as a prebiotic source of phosphorus. While previous studies looking into the formation of these alkylphosphonic acids have focused on the iron-nickel phosphide mineral schreibersite and phosphorous acid as a source of phosphorus, this work utilizes phosphine (PH3), which has been discovered in the circumstellar envelope of IRC +10216, in the atmosphere of Jupiter and Saturn, and believed to be the phosphorus carrier in comet 67P/Churyumov-Gerasimenko. Phosphine ices prepared with interstellar molecules such as carbon dioxide, water, and methane were subjected to electron irradiation, which simulates the secondary electrons produced from galactic cosmic rays penetrating the ice, and probed using infrared spectroscopy to understand the possible formation of alkylphosphonic acids and their precursors on interstellar icy grains that could become incorporated into meteorites such as Murchison. We present the first study and results on the possible synthesis of alkylphosphonic acids produced from phosphine-mixed ices under interstellar conditions. All functional groups of alkylphosphonic acids were detected through infrared spectroscopically, suggesting that this class of molecules can be formed in interstellar ices.

On the Synthesis of Chocolate Flavonoids (Propanols, Butanals) in the Interstellar Medium

Complex organic molecules are ubiquitous in star- and planet-forming regions as well as on comets such as on 67P/Churyumov-Gerasimenko, but their origins have remained largely unexplained until now. Here, we report the first laboratory detection of distinct C3 H8 O (propanol, methyl ethyl ether) and C4 H8 O (n-butanal, i-butanal) isomers formed within interstellar analog ices through interaction with ionizing radiation. This study reveals that complex organics with propyl (C3 H7 ) and butyl (C4 H9 ) groups can be synthesized easily in deep space and may act as key evolutionary tracers of a cosmic ray driven non-equilibrium chemistry in low temperature interstellar ices at 10 K. These processes are of vital importance in initiating a chain of chemical reactions leading to complex organics-some of which are responsible for the flavors of chocolate-not only in the interstellar medium, but also on comet 67P/Churyumov-Gerasimenko.

An interstellar synthesis of phosphorus oxoacids

Phosphorus signifies an essential element in molecular biology, yet given the limited solubility of phosphates on early Earth, alternative sources like meteoritic phosphides have been proposed to incorporate phosphorus into biomolecules under prebiotic terrestrial conditions. Here, we report on a previously overlooked source of prebiotic phosphorus from interstellar phosphine (PH3) that produces key phosphorus oxoacids—phosphoric acid (H3PO4), phosphonic acid (H3PO3), and pyrophosphoric acid (H4P2O7)—in interstellar analog ices exposed to ionizing radiation at temperatures as low as 5 K. Since the processed material of molecular clouds eventually enters circumstellar disks and is partially incorporated into planetesimals like proto Earth, an understanding of the facile synthesis of oxoacids is essential to untangle the origin of water-soluble prebiotic phosphorus compounds and how they might have been incorporated into organisms not only on Earth, but potentially in our universe as well.Extraterrestrial sources may have provided prebiotic phosphorus to the early Earth. Here, the authors investigate the potential of phosphine-doped astrochemical analog ices to form phosphorus oxoacids as precursors to more complex prebiotic compounds.