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All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

Propynal, an Interstellar Molecule with an Exceptionally Strong C≡C Infrared Band - Laboratory Infrared Data and Applications

Isomers with the formula C3H2O have intrigued and puzzled astronomers and astrochemists for many years, with propynal and cyclopropenone, but not propadienone, known to be interstellar. However, there is a severe lack of laboratory spectra of the solid phases of these compounds with which to investigate their interstellar chemistry. Here we present the first infrared spectra of amorphous and crystalline forms of propynal, HCC-C(O)H, at multiple temperatures. Band positions are tabulated and band strengths are derived in terms of absorption coefficients and integrated intensities. Optical constants are calculated for amorphous propynal, refractive indices are measured, and densities are estimated. Three laboratory astrochemistry applications are described, including a new spectral identification in an earlier paper. It is shown that propynal's C≡C infrared absorbance is about 30,000% stronger than the corresponding feature in acetylene. This band's intensity and spectral position make it an attractive candidate for astronomical searches involving interstellar ices.

astrochemistry – ISM: molecules↗
NASA NTRS2018

Propynal, an Interstellar Molecule with an Exceptionally Strong C≡C Infrared Band - Laboratory Infrared Data and Applications

Isomers with the formulaC3H2Ohave intrigued and puzzled astronomers and astrochemists for many years, with propynal and cyclopropenone, but not propadienone, known to be interstellar. However, there is a severe lack of laboratory spectra of the solid phases of these compounds with which to investigate their interstellar chemistry. Here we present the first infrared spectra of amorphous and crystalline forms of propynal, HCC C(O)H, at multiple temperatures. Band positions are tabulated and band strengths are derived in terms of absorption coefficients and integrated intensities. Optical constants are calculated for amorphous propynal, refractive indices aremeasured, and densities are estimated. Three laboratory astrochemistry applications are described, including a new spectral identification in an earlier paper. It is shown that propynal’s C C infrared absorbance is about 30 000 per cent stronger than the corresponding feature in acetylene. This band’s intensity and spectral position make it an attractive candidate for astronomical searches involving interstellar ices.

astrochemistry – ISM: molecules↗
DOE OSTI2023

The P( 4 S) + NH( 3 Σ – ) and N( 4 S) + PH( 3 Σ – )reactions as sources of interstellar phosphorus nitride

Phosphorus nitride (PN) is believed to be one of the major reservoirs of phosphorus in the interstellar medium (ISM). For this reason, understanding which reactions produce PN in space and predicting their rate coefficients is important for modelling the relative abundances of P-bearing species and clarifying the role of phosphorus in astrochemistry. Here, in this work, we explore the potential energy surfaces of the $\textrm{P}(^4\textrm{S}) + \textrm{NH}(^3\Sigma^-)$ and $\textrm{N}(^4\textrm{S}) + \textrm{PH}(^3\Sigma^-)$ reactions and the formation of $\textrm{H}(^2\textrm{S}) + \textrm{PN}(^1\Sigma^+)$ through high accuracy ab initio calculations and the variable reaction coordinate transition state theory (VRC-TST). We found that both reactions proceed without an activation barrier and with similar rate coefficients that can be described by a modified Arrhenius equation ( $k(T)=\alpha\!\left( T/300 \right)^{\beta} \exp\!{(\!-\!\gamma/T)})$ with $\alpha=0.93\times 10^{-10}\rm cm^3\,s^{-1}$ , $\beta=-0.18$ and $\gamma=0.24\, \rm K$ for the $\textrm{P} + \textrm{NH} \longrightarrow \textrm{H} + \textrm{PN}$ reaction and $\alpha=0.88\times 10^{-10}\rm cm^3\,s^{-1}$ , $\beta=-0.18$ and $\gamma=1.01\, \rm K$ for the $\textrm{N} + \textrm{PH} \longrightarrow \textrm{H} + \textrm{PN}$ one. Both reactions are expected to be relevant for modelling PN abundances even in the cold environments of the ISM. Given the abundance of hydrogen in space, we have also predicted rate coefficients for the destruction of PN via H + PN collisions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics

ConspectusThe study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 1016-1018 cm-3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical-radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C3H3 reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical-radical reactions. We determined the product branching in the C3H2 isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an extended Laval nozzle, after which a shock-free secondary expansion to low temperature and density affords an ideal environment for detection by rotational spectroscopy. These results highlight the power and potential of the CPUF approach, and future prospects will also be discussed in light of these developments.

Dias, Nureshan↗
DOE OSTI2025

An Unconventional Dark Radical Chemistry in Dense Molecular Clouds: Directed Gas-Phase Formation of Naphthyl Radicals

The synthetic pathways to aromatic molecules inside photon-shielded dense molecular clouds remain a fundamental, unsolved enigma in astrochemistry and astrophysics, with low-temperature molecular growth routes involving aromatic radicals, such as prototype bicyclic naphthyl (C 10 H 7 • ), implicated as key sources. Here, exploiting crossed molecular beam experiments augmented by electronic structure calculations, unexpected pathways are exposed leading to the gas-phase formation of 1- and 2-naphthyl via barrierless bimolecular reactions of atomic carbon (C) with indene (C 9 H 8 ) and of dicarbon (C 2 ) with styrene (C 8 H 8 ) accompanied by ring expansion and cyclization together with aromatization. These facile routes challenge conventional wisdom that aromatic radicals are formed in deep space solely via “bright” gas-phase photochemistry of their closed-shell polycyclic aromatic hydrocarbon (PAH) precursors. A hitherto disregarded “dark” aromatic radical chemistry with aromatic radicals synthesized via gas-phase reactions offers new concepts on the chemical evolution of the chemistry of dark molecular clouds eventually culminating in the rapid formation of aromatics, fullerenes, and carbonaceous nanostructures.

Aromatic compounds↗
DOE OSTI2024

Reaction dynamics of S( 3 P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S( 3 P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H 2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C 3 H 4 S (loss of ethene or H 2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Lang, Jinxin↗
DOE OSTI2023

Collisional excitation of C2H− by H2: New interaction potential and scattering calculations

Interstellar anions play an important role in astrochemistry as being tracers of the physical and chemical conditions in cold molecular clouds and circumstellar gas. The local thermodynamic equilibrium is generally not fulfilled in media where anions are detected and radiative and collisional data are required to model the observed lines. The C2H− anion has not yet been detected in the interstellar medium; however, collisional data could be used for non-LTE models that would help in identifying the most intense lines. For this purpose, we have computed the first 4D potential energy surface (PES) of the C2H−–H2 complex using an explicitly correlated coupled-cluster approach. The PES is characterized by a single deep minimum with a well-depth of 924.96 cm−1. From this interaction potential, we derived excitation cross sections and rate coefficients of C2H− induced by collisions with para- and ortho-H2. The results obtained for collisions with para-H2 are compared to previous calculations performed using a 2D-PES obtained from an average over H2 rotations.

Chemistry↗
DOE OSTI2022

All-optical nanoscopic spatial control of molecular reaction yields on nanoparticles

Molecular adsorbate reactions on nanoparticles play a fundamental role in areas such as nano-photocatalysis, atmospheric, and astrochemistry. They can be induced, enhanced, and controlled by field localization and enhancement on the nanoparticle surface. In particular, the ability to perform highly controlled near-field-mediated reactions is key to deepening our understanding of surface photoactivity on nanosystems. Here, using reaction nanoscopy, we experimentally demonstrate all-optical nanoscopic control of surface reaction yields by tailoring the near fields on nanoparticles with waveform-controlled linear and bicircular two-color laser pulses, respectively. We observe site-selective proton emission from the dissociative ionization of adsorbate molecules on Si O 2 nanoparticles as a function of the polarization and relative phase of the two-color pulses. The angularly resolved close-to-uniform mapping between the surface reaction yields and the measured ion momentum enables the observation and spatial control of molecular reactions on the nanoparticle surface with nanoscopic resolution. The experimental results are modeled and reproduced qualitatively by classical trajectory Monte Carlo simulations. Our work paves the way toward reliable all-optical control of photocatalytic chemical reactions on nanoscale surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Theoretical studies of chemical reactions related to the formation and growth of polycyclic aromatic hydrocarbons (PAH) and molecular properties of their key intermediates (Final Progress Report)

The formation mechanisms of polycyclic aromatic hydrocarbons, (PAHs) – organic molecules carrying fused benzene rings – are of great interest to scientists and engineers due to their importance in combustion chemistry and astrochemistry. On Earth, PAHs are largely produced in incomplete combustion of fossil fuel and are considered as critical precursors to unwanted soot particles leading to combustion inefficiency and causing air pollution along with detrimental health effects. Simple PAH molecules initially formed in the gas phase, are further involved in a build-up process in combustion flames leading to larger PAH, bowl-shaped nanostructures, fullerenes, and solid-phase species including carbonaceous dust, graphene particles, and soot. In deep space, PAH and their derivatives are potential key intermediates and nucleation sites leading eventually to carbonaceous nanoparticles (“interstellar grains”). Therefore, the understanding of the key processes in the synthesis of PAHs along with their precursors and their degradation mechanisms in combustion systems and in interstellar, circumstellar, and planetary atmospheric environments will provide critical insights into how complex aromatic structures, carbonaceous nanoparticles, and fullerenes are formed and destroyed. Achieving this understanding is an important step in the development of the efficient combustion processes and of the ecofriendly devices with reduced environmental pollution as well as technological strategies for the production of hydrogen and solid carbon through thermal or plasma-assisted pyrolysis of natural gas and biomass. Also, the understanding of the key processes of PAH and soot growth will help in our comprehension of chemical evolution in the universe. Detailed information on the mechanisms and reliable rate constants of the key elementary chemical reactions involved in PAH formation and destruction processes and in inception of soot particles is often missing, with the main deficiencies being the absence of temperature- and pressure-dependent rate constants for the broad range of conditions occurring in various terrestrial and interstellar processes and the lack of data on the reaction products and their branching ratios. Complementary to experimental studies, these gaps in knowledge can be filled by using quantum chemical calculations of reaction potential energy surfaces providing us with accurate energies of reaction products, intermediates, and transition states, revealing the reaction mechanism, and giving the molecular properties required to compute rate constants for relevant reaction steps and product branching ratios using the RRKM-Master Equation (ME) method. Molecular dynamics (MD) simulations can be used in cases when a reaction rate cannot be properly described by statistical theories. During the terminal renewal project period we employed these ab initio/RRKM-ME and MD approaches to complete our studies on several key reactions relevant to the formation/growth of PAH and inception of soot particles including (1) the reaction mechanism and kinetics of the resonance stabilized fulvenallenyl radical with propargyl and C 3 H 4 isomers; (2) the reaction mechanism and kinetics for the C + indene and C 2 + styrene reactions producing naphthyl or azulenyl radicals in low-temperature environments; (3) the MD study of non-equilibrium dimerization of acepyrene and coronene and its radical. The information derived from our theoretical calculations contributed to a better fundamental understanding of the reaction mechanisms and provide missing critical kinetic data to improve combustion models of hydrocarbon fuels and astrochemical models of the growth of carbonaceous molecules and particles in cold molecular clouds, circumstellar envelopes, and planetary atmospheres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Boundary conditions for the paleoenvironment: Chemical and Physical Processes in dense interstellar clouds

The present research includes searches for important new interstellar constituents; observations relevant to differentiating between different models for the chemical processes that are important in the interstellar environment; and coordinated studies of the chemistry, physics, and dynamics of molecular clouds which are the sites or possible future sites of star formation. Recent research has included the detection and study of four new interstellar molecules; searches which have placed upper limits on the abundance of several other potential constituents of interstellar clouds; quantitative studies of comparative molecular abundances in different types of interstellar clouds; investigation of reaction pathways for astrochemistry from a comparison of theory and the observed abundance of related species such as isomers and isotopic variants; studies of possible tracers of energenic events related to star formation, including silicon and sulfur containing molecules; and mapping of physical, chemical, and dynamical properties over extended regions of nearby cold molecular clouds.

Irvine, W. M.↗
NASA NTRS1987

Far-infrared and submillimeter observations of interstellar clouds

Research in the use of FIR and sub-mm lines to provide data relevant to astrochemistry is examined. Spectroscopic features in the FIR and sub-mm are dominated by transitions from species of atoms and atomic ions, metal hydrides, and heavy molecules. The data of Lester et al.(1983) and Dinerstein et al. (1984) on the N/O abundance ratio are discussed. The N/O abundance ratio is analyzed as a function of the galactic radius, and the procedure for determining the N/O abundance ratio from the FIR and sub-mm lines is given. The conditions at the surface of molecular clouds and the chemical profile of molecular clouds are studied in the forbidden lines O I 63.18 and 145.53 microns and the forbidden line C II 157.74 microns. Results of recent FIR/sub-mm observations of post-shocked gas which relate to modeling the chemical processing that occurs in the wake of shock waves are considered.

Melnick, Gary↗
NASA NTRS1990

Interstellar cyanomethane

An observational study was made of the newly identified cyanomethane radical CH2CN and the possibly related species CH3CN with the goals of elucidating the possible role of reactions of the type CnHm(+) + N in astrochemistry, and providing a possible test of Bates's models of dissociative electron recombination. A remarkably different abundance ratio CH2CN/CH3CN was found in TMC-1 and Sgr B2 which is deduced to be a result of the large difference in temperature of these objects. Studies of CH2CN and CH3CN in other sources, including two new detections of CH2CN, support this conclusion and are consistent with a monotonic increase in the CH2CN/CH3CN ratio with decreasing temperature over the range 10-120 K. This behavior may be explained by the destruction of CH2CN by reaction with O.

Turner, B. E.↗
NASA NTRS1991

Theoretical studies of the extraterrestrial chemistry of biogenic elements and compounds

Organic compounds, molecules related to those in living systems, are found in many different extraterrestrial environments. The study of organic astrochemistry is important to exobiology both because it demonstrates the ubiquity of processes which led to life on Earth and because the dust clouds where molecules are found are analogs of the solar nebula from which the Earth formed. In the long chain of events leading from the Big Bang, and a universe composed of atomic hydrogen and helium, to the emergence of life on Earth, molecular interstellar clouds are an early link, the most primitive objects which display any significant organic chemistry. One such cloud was the direct precursor to the solar system and to all objects which it contains. Theoretical methods are ideally suited to studying interstellar cloud chemistry. They have been applied to determine spectroscopic constants of candidate interstellar molecules, mechanisms of ion-molecule reactions, and composition of dust grains. Accurate predictions of rotational constants and dipole moments of long-chain carbon molecules HC13N, HC15N, and C5O have been made to aid in determining the size limit of gas-phase interstellar molecules. Models of gas-phase interstellar chemistry use reaction rate constants measured at room temperature and extrapolated to interstellar temperatures. The temperature dependence of NH3(+)+H2 yields NH4(+)+H is anomalous, however, with a minimum rate at about 100K, casting doubt on the extrapolation procedures. The temperature dependence has now been explained.

Defrees, D. J.↗
NASA NTRS1996

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 (approx. 0.5 kcal/mole), 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. 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.

Woon, David E.↗
NASA NTRS1997

Boundary Conditions for the Paleoenvironment: Chemical and Physical Processes in the Pre-Solar Nebula

The basic theme of this program is the study of molecular complexity and evolution in interstellar clouds and in primitive solar system objects. Research has included the detection and study of a number of new interstellar molecules and investigation of reaction pathways for astrochemistry from a comparison of theory and observed molecular abundances. The latter includes studies of cold, dark clouds in which ion-molecule chemistry should predominate, searches for the effects of interchange of material between the gas and solid phases in interstellar clouds, unbiased spectral surveys of particular sources, and systematic investigation of the interlinked chemistry and physics of dense interstellar clouds. In addition, the study of comets has allowed a comparison between the chemistry of such minimally thermally processed objects and that of interstellar clouds, shedding light on the evolution of the biogenic elements during the process of solar system formation.

Irvine, William M.↗
NASA NTRS1998

The Identification of Complex Organic Molecules in the Interstellar Medium: Using Lasers and Matrix Isolation Spectroscopy to Simulate the Interstellar Environment

The Astrochemistry Group at NASA Ames Research Center is interested in the identification of large organic molecules in the interstellar medium Many smaller organic species (e.g. hydrocarbons, alcohols, etc.) have been previously identified by their radiofrequency signature due to molecular rotations. However, this becomes increasingly difficult to observe as the size of the molecule increases. Our group in interested in the identification of the carriers of the Diffuse Interstellar Bands (absorption features observed throughout the visible and near-infrared in the spectra of stars, due to species in the interstellar medium). Polycyclic Aromatic Hydrocarbons (PAHs) and related molecules are thought to be good candidates for these carriers. Laboratory experiments am performed at Ames to simulate the interstellar environment, and to compare spectra obtained from molecules in the laboratory to those derived astronomically. We are also interested in PAHs with respect to their possible connection to the UIR (Unidentified infrared) and ERE (Extended Red Emission) bands - emission features found to emanate from particular regions of our galaxy (e.g. Orion nebula, Red Rectangle, etc.). An old, "tried and proven spectroscopic technique, matrix isolation spectroscopy creates molecular conditions ideal for performing laboratory astrophysics.

Stone, Bradley M.↗
NASA NTRS1999

Boundary Conditions for the Paleoenvironment: Chemical and Physical Processes in Dense Interstellar Clouds: Summary of Research

The basic theme of this program was the study of molecular complexity and evolution for the biogenic elements and compounds in interstellar clouds and in primitive solar system objects. Research included the detection and study of new interstellar and cometary molecules and investigation of reaction pathways for astrochemistry from a comparison of theory and observed molecular abundances. The latter includes studies of cold, dark clouds in which ion-molecule chemistry should predominate, searches for the effects of interchange of material between the gas and solid phases in interstellar clouds, unbiased spectral surveys of particular sources, and systematic investigation of the interlinked chemistry and physics of dense interstellar clouds. In addition, the study of comets has allowed a comparison between the chemistry of such minimally thermally processed objects and that of interstellar clouds, shedding light on the evolution of the biogenic elements during the process of solar system formation. One PhD dissertation on this research was completed by a graduate student at the University of Massachusetts. An additional 4 graduate students at the University of Massachusetts and 5 graduate students from other institutions participated in research supported by this grant, with 6 of these thus far receiving PhD degrees from the University of Massachusetts or their home institutions. Four postdoctoral research associates at the University of Massachusetts also participated in research supported by this grant, receiving valuable training.

Irvine, William M.↗