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Reggie L Hudson

Publications and source records attributed to Reggie L Hudson.

14 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2022

Radiation-induced D/H Exchange Rate Constants in Aliphatics Embedded in Water Ice

Gas-phase and solid-state chemistry in low-temperature interstellar clouds and cores leads to a D/H enhancement in interstellar ices, which is eventually inherited by comets, meteorites, and even planetary satellites. Hence, the D/H ratio has been widely used as a tracer for the origins of extraterrestrial chemistry. However, the D/H ratio can also be influenced by cosmic rays, which are ubiquitous and can penetrate even dense interstellar molecular cores. The effects of such high-energy radiation on deuterium fractionation have not been studied in a quantitative manner. In this study, we present rate constants for radiation-induced D-to-H exchange for fully deuterated small (1–2 C) hydrocarbons embedded in H2O ice at 20 K and H-to-D exchange for the protiated forms of these molecules in D2O ice at 20 K. We observed larger rate constants for H-to-D exchange in the D2O ice versus D-to-H exchange in H2O ice, which we have attributed to the greater bond strength of C–D versus C–H. We find that the H-to-D exchange rate constants are smaller for protiated methane than ethane, in agreement with bond energies from the literature. We are unable to obtain rate constants for the unsaturated and reactive hydrocarbons ethylene and acetylene. Interpretation of the rate constants suggest that D/H exchange products are formed in abundance alongside radiolysis products. We discuss how our quantitative and qualitative data can be used to interpret the D/H ratios of aliphatic compounds observed throughout space.

Ice destruction↗
NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗
NASA NTRS2020

Laboratory Studies of Astronomical Ices: Reaction Chemistry and Spectroscopy

In this article, we will describe the work of the Cosmic Ice Laboratory at NASA’s Goddard Space Flight Center to characterize the composition of and to understand the chemistry occurring in icy bodies in the Solar System and beyond. Our work has touched on a wide range of extraterrestrial environments including icy interstellar grains, small bodies such as comets and asteroids, and planets and moons. We are especially interested in the chemical and physical changes that occur in ices as a result of thermal changes or exposure to radiation. To this end, we conduct experiments designed to simulate cold extraterrestrial environments and measure physical properties of single- and multi-component ices. We expose ices to radiation (e.g., MeV protons or keV-MeV electrons) or high-energy photons (e.g., UV) to initiate physical and chemical changes. We conduct experiments using cryo-vacuum chambers equipped with analytical tools and radiation sources to make most of our measurements, including the collection of all spectroscopic data,in situ. When possible and appropriate, we also collect reaction products for further ex situ analysis. The work of the Cosmic Ice Lab provides critical data to astrochemists and others seeking to understand observations, make predictions, and plan future space missions.

Christopher K Materese↗
NASA NTRS2020

Infrared Spectra and Optical Constants of Astronomical Ices: III. Propane, Propylene, and Propyne

Infrared (IR) spectra of the hydrocarbon ices C3H8 (propane), C3H6 (propylene, propene), and C3H4 (propyne, methylacetylene) are relevant to the study of the low-temperature chemistry and spectroscopy of objects within and beyond the Solar System, but IR band strengths and absorption coefficients are lacking for these compounds. Here we present new IR spectra of crystalline and non-crystalline forms of C3H8, C3H6, and C3H4. Measurements of ice density and refractive index also are reported, two quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, abundances of propane, propylene, and propyne in extraterrestrial environments and in laboratory experiments. Suggestions and interpretations are offered regarding the multiple crystalline forms of propane and propylene observed. Applications and extensions are described.

Reggie L Hudson↗
NASA NTRS2020

The Radiation Stability of Thymine in Solid H2O

Nucleobases are of significant importance to all known organisms, may be an important building block of life, and could be important biosignatures of current or past life. Given their potential significance to the field of astrobiology, it is important to understand the survival of these molecules when subjected to ionizing radiation as is present in a range of extraterrestrial environments. In this work we present data on the kinetics of the radiolytic destruction of pure thymine, and water + thymine ice mixtures at temperatures from 13 to 150 K. Rate constants were measured using in situ infrared spectroscopy and radiolytic half-lives for thymine were computed for different planetary and interstellar environments. Our results demonstrate that the survival of thymine decreases as the dilution of thymine in water increases. Additionally, we find that thymine survival increases with ice temperature and that this decrease may be related to structure of the ice matrix.

nucleobases, radiolysis, astrobiology↗
NASA NTRS2019

Preparation, Identification, and Low-Temperature Infrared Spectra of Two Elusive Crystalline Nitrile Ices

Infrared (IR) spectra of the alkyl nitrile ices CH3CN and CH3CH2CN are relevant to the study of the low-temperature chemistry of objects within and beyond the Solar System, but the thermodynamically favored low-temperature crystalline phases of these compounds have not been presented and identified in the planetary-sciences literature. Moreover, there is a large variation in the published IR spectra of these two icy solids, including spectra that are used for the analyses of spacecraft data from the Voyager and Cassini missions. Here the IR spectra of the low-temperature crystalline forms of CH3CN and CH3CH2CN, which are the thermodynamically stable phases at Titan temperatures, are presented for the first time with all samples being made by vapor-phase deposition. Conditions are described for producing these ice phases for both compounds, and new measurements are reported of ice density and refractive index, quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, nitrile abundances in extraterrestrial environments. Comparisons are drawn between CH3CN and CH3CH2CN, an earlier prediction on their similar crystallization behaviors is verified, and previous work is examined in light of these new results, including a counter-intuitive observation in which the low-temperature phase of an ice is made by heating a high-temperature phase. Applications and extensions are described.

Reggie L Hudson↗
NASA NTRS2019

Preparation, Identification, and Low-Temperature Infrared Spectra of Two Elusive Crystalline Nitrile Ices

Infrared (IR) spectra of the alkyl nitrile ices CH3CN and CH3CH2CN are relevant to the study of the low-temperature chemistry of objects within and beyond the Solar System, but the thermodynamically favored low-temperature crystalline phases of these compounds have not been presented and identified in the planetary-sciences literature. Moreover, there is a large variation in the published IR spectra of these two icy solids, including spectra that are used for the analyses of spacecraft data from the Voyager and Cassini missions. Here the IR spectra of the low-temperature crystalline forms of CH3CN and CH3CH2CN, which are the thermodynamically stable phases at Titan temperatures, are presented for the first time with all samples being made by vapor-phase deposition. Conditions are described for producing these ice phases for both compounds, and new measurements are reported of ice density and refractive index, quantities needed to compute IR absorption coefficients, band strengths, optical constants, and, ultimately, nitrile abundances in extraterrestrial environments. Comparisons are drawn between CH3CN and CH3CH2CN, an earlier prediction on their similar crystallization behaviors is verified, and previous work is examined in light of these new results, including a counter-intuitive observation in which the low-temperature phase of an ice is made by heating a high-temperature phase. Applications and extensions are described.

Ices, IR spectroscopy, Titan, organic chemistry, i↗
NASA NTRS2019

Solid-State Isomerization and Infrared Band Strengths of Two Conformational Isomers of Cyclopropanecarboxaldehyde, A Candidate Interstellar Molecule

At least a dozen of the known interstellar molecules possess a formyl group (HCO), suggesting that other such species exist and await discovery in the interstellar medium. Here, we examine the mid-infrared (mid-IR) spectrum and selected physical properties of one such candidate, cyclopropanecarboxaldehyde, in amorphous ices. Mid-IR transmission spectra of solid cyclopropanecarboxaldehyde are presented for the first time and used to determine the cis-to-trans ratio of conformational isomers present in amorphous samples. The measured ratio is compared to one from an electron-diffraction study of the gas-phase compound. The cis-to-trans isomerization in the amorphous compound is followed, and the activation energy is determined. The first IR band strengths for solid cyclopropanecarboxaldehyde are reported. Also presented are refractive indices and densities at 15 K for amorphous forms of two related compounds, cyclopropane and cyclopropanemethanol. Two low-temperature reactions for the interstellar formation of cyclopropanecarboxaldehyde are briefly described.

band strengths↗
NASA NTRS2018

Infrared Spectra and Interstellar Sulfur: New Laboratory Results for H2S and Four Malodorous Thiol Ices

New infrared spectra are presented for H2S and four other sulfur-containing compounds, all thiols, at 10–140 K to aid in the study of interstellar and solar system ices. Infrared spectral changes on warming H2S and each thiol are described with an emphasis on the S–H stretching vibration at 2550–2525 cm(exp −1) (λ = 3.92–3.96 μm) as it is in a relatively unobscured part of the infrared spectra of interstellar and planetary ices. Infrared positions and band strengths for each thiol’s S–H and C–H stretching vibrations are reported, along with the S–H band strength of H2S. Two band strengths of near-infrared features of CH3SH are included. Results for these compounds are compared, and some areas of agreement and disagreement with the literature are described.

Astrochemistry; infrared: ISM; ISM: molecules; mol↗
NASA NTRS2018

Infrared Spectra and Interstellar Sulfur - New Laboratory Results for H2S and Four Malodorous Thiol Ices

New infrared spectra are presented for H2S and four other sulfur-containing compounds, all thiols, at 10–140 K to aid in the study of interstellar and solar system ices. Infrared spectral changes on warming H2S and each thiol are described with an emphasis on the S–H stretching vibration at 2550–2525 cm(exp −1) (λ = 3.92–3.96 μm) as it is in a relatively unobscured part of the infrared spectra of interstellar and planetary ices. Infrared positions and band strengths for each thiol’s S–H and C–H stretching vibrations are reported, along with the S–H band strength of H2S. Two band strengths of near-infrared features of CH3SH are included. Results for these compounds are compared, and some areas of agreement and disagreement with the literature are described.

Astrochemistry; infrared: ISM; ISM: molecules; mol↗
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↗
NASA NTRS2015

The Radiation Stability of Glycine in Solid CO2 - In Situ Laboratory Measurements with Applications to Mars

The detection of biologically important, organic molecules on Mars is an important goal that may soon be reached. However, the current small number of organic detections at the martian surface may be due to the harsh UV and radiation conditions there. It seems likely that a successful search will require probing the subsurface of Mars, where penetrating cosmic rays and solar energetic particles dominate the radiation environment, with an influence that weakens with depth. Toward the goal of understanding the survival of organic molecules in cold radiation-rich environments on Mars, we present new kinetics data on the radiolytic destruction of glycine diluted in frozen carbon dioxide. Rate constants were measured in situ with infrared spectroscopy, without additional sample manipulation, for irradiations at 25, 50, and 75 K with 0.8-MeV protons. The resulting half-lives for glycine in CO2-ice are compared to previous results for glycine in H2O-ice and show that glycine in CO2-ice is much less stable in a radiation environment, with destruction rate constants approximately 20-40 times higher than glycine in H2O-ice. Extrapolation of these results to conditions in the martian subsurface results in half-lives estimated to be less than 100-200 Myr even at depths of a few meters.

Ices↗