73 research outputs found
CO Infrared Phonon Modes in Interstellar Ice Mixtures
CO ice is an important reservoir of carbon and oxygen in star and planet
forming regions. Together with water and CO, CO sets the physical and
chemical characteristics of interstellar icy grain mantles, including
desorption and diffusion energies for other ice constituents. A detailed
understanding of CO ice spectroscopy is a prerequisite to characterize
CO interactions with other volatiles both in interstellar ices and in
laboratory experiments of interstellar ice analogs. We report laboratory
spectra of the CO longitudinal optical (LO) phonon mode in pure CO ice
and in CO ice mixtures with HO, CO, O components. We show that the
LO phonon mode position is sensitive to the mixing ratio of various ice
components of astronomical interest. In the era of JWST, this characteristic
could be used to constrain interstellar ice compositions and morphologies. More
immediately, LO phonon mode spectroscopy provides a sensitive probe of ice
mixing in the laboratory and should thus enable diffusion measurements with
higher precision than has been previously possible
Benzonitrile as a Proxy for Benzene in the Cold ISM: Low-temperature Rate Coefficients for CN + C₆H₆
The low-temperature reaction between CN and benzene (C₆H₆) is of significant interest in the astrochemical community due to the recent detection of benzonitrile, the first aromatic molecule identified in the interstellar medium (ISM) using radio astronomy. Benzonitrile is suggested to be a low-temperature proxy for benzene, one of the simplest aromatic molecules, which may be a precursor to polycyclic aromatic hydrocarbons. In order to assess the robustness of benzonitrile as a proxy for benzene, low-temperature kinetics measurements are required to confirm whether the reaction remains rapid at the low gas temperatures found in cold dense clouds. Here, we study the C₆H₆ + CN reaction in the temperature range 15–295 K, using the well-established CRESU technique (a French acronym standing for Reaction Kinetics in Uniform Supersonic Flow) combined with pulsed-laser photolysis-laser-induced fluorescence. We obtain rate coefficients, k(T), in the range (3.6–5.4) × 10⁻¹⁰ cm³ s⁻¹ with no obvious temperature dependence between 15 and 295 K, confirming that the CN + C₆H₆ reaction remains rapid at temperatures relevant to the cold ISM
CO diffusion and desorption kinetics in CO ices
Diffusion of species in icy dust grain mantles is a fundamental process that
shapes the chemistry of interstellar regions; yet measurements of diffusion in
interstellar ice analogs are scarce. Here we present measurements of CO
diffusion into CO ice at low temperatures (T=11--23~K) using CO
longitudinal optical (LO) phonon modes to monitor the level of mixing of
initially layered ices. We model the diffusion kinetics using Fick's second law
and find the temperature dependent diffusion coefficients are well fit by an
Arrhenius equation giving a diffusion barrier of 300 40 K. The low
barrier along with the diffusion kinetics through isotopically labeled layers
suggest that CO diffuses through CO along pore surfaces rather than through
bulk diffusion. In complementary experiments, we measure the desorption energy
of CO from CO ices deposited at 11-50 K by temperature-programmed
desorption (TPD) and find that the desorption barrier ranges from 1240 90
K to 1410 70 K depending on the CO deposition temperature and
resultant ice porosity. The measured CO-CO desorption barriers demonstrate
that CO binds equally well to CO and HO ices when both are compact. The
CO-CO diffusion-desorption barrier ratio ranges from 0.21-0.24 dependent on
the binding environment during diffusion. The diffusion-desorption ratio is
consistent with the above hypothesis that the observed diffusion is a surface
process and adds to previous experimental evidence on diffusion in water ice
that suggests surface diffusion is important to the mobility of molecules
within interstellar ices
Benzonitrile as a Proxy for Benzene in the Cold ISM: Low-temperature Rate Coefficients for CN + C₆H₆
The low-temperature reaction between CN and benzene (C₆H₆) is of significant interest in the astrochemical community due to the recent detection of benzonitrile, the first aromatic molecule identified in the interstellar medium (ISM) using radio astronomy. Benzonitrile is suggested to be a low-temperature proxy for benzene, one of the simplest aromatic molecules, which may be a precursor to polycyclic aromatic hydrocarbons. In order to assess the robustness of benzonitrile as a proxy for benzene, low-temperature kinetics measurements are required to confirm whether the reaction remains rapid at the low gas temperatures found in cold dense clouds. Here, we study the C₆H₆ + CN reaction in the temperature range 15–295 K, using the well-established CRESU technique (a French acronym standing for Reaction Kinetics in Uniform Supersonic Flow) combined with pulsed-laser photolysis-laser-induced fluorescence. We obtain rate coefficients, k(T), in the range (3.6–5.4) × 10⁻¹⁰ cm³ s⁻¹ with no obvious temperature dependence between 15 and 295 K, confirming that the CN + C₆H₆ reaction remains rapid at temperatures relevant to the cold ISM
Rate Constants of the CN + Toluene Reaction from 15 – 294 K and Interstellar Implications
CN is known for its fast reactions with hydrocarbons at low temperatures, but relatively few studies have focused on the reactions between CN and aromatic molecules. The recent detection of benzonitrile in the interstellar medium, believed to be produced by the reaction of CN and benzene, has ignited interest in studying these reactions. Here, we report rate constants of the CN + toluene (C₇H₈) reaction between 15 and 294 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme; reaction kinetics in uniform supersonic flow) apparatus coupled with the pulsed laser photolysis–laser-induced fluorescence (PLP–LIF) technique. We also present the stationary points on the potential energy surface of this reaction to study the available reaction pathways. We find the rate constant does not change over this temperature range, with an average value of (4.1 ± 0.2) × 10⁻¹⁰ cm³ s⁻¹, which is notably faster than the only previous measurement at 105 K. While the reason for this disagreement is unknown, we discuss the possibility that it is related to enhanced multiphoton effects in the previous work
Rate Constants of the CN + Toluene Reaction from 15 – 294 K and Interstellar Implications
CN is known for its fast reactions with hydrocarbons at low temperatures, but relatively few studies have focused on the reactions between CN and aromatic molecules. The recent detection of benzonitrile in the interstellar medium, believed to be produced by the reaction of CN and benzene, has ignited interest in studying these reactions. Here, we report rate constants of the CN + toluene (C₇H₈) reaction between 15 and 294 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme; reaction kinetics in uniform supersonic flow) apparatus coupled with the pulsed laser photolysis–laser-induced fluorescence (PLP–LIF) technique. We also present the stationary points on the potential energy surface of this reaction to study the available reaction pathways. We find the rate constant does not change over this temperature range, with an average value of (4.1 ± 0.2) × 10⁻¹⁰ cm³ s⁻¹, which is notably faster than the only previous measurement at 105 K. While the reason for this disagreement is unknown, we discuss the possibility that it is related to enhanced multiphoton effects in the previous work
Astrochemical Modeling of Propargyl Radical Chemistry in TMC-1
Recent detections of aromatic species in dark molecular clouds suggest
formation pathways may be efficient at very low temperatures and pressures, yet
current astrochemical models are unable to account for their derived
abundances, which can often deviate from model predictions by several orders of
magnitude. The propargyl radical, a highly abundant species in the dark
molecular cloud TMC- 1, is an important aromatic precursor in combustion flames
and possibly interstellar environments. We performed astrochemical modeling of
TMC-1 using the three-phase gas-grain code NAUTILUS and an updated chemical
network, focused on refining the chemistry of the propargyl radical and related
species. The abundance of the propargyl radical has been increased by half an
order of magnitude compared to the previous GOTHAM network. This brings it
closer in line with observations, but it remains underestimated by two orders
of magnitude compared to its observed value. Predicted abundances for the
chemically related C4H3N isomers within an order of magnitude of observed
values corroborate the high efficiency of CN addition to closed-shell
hydrocarbons under dark molecular cloud conditions. The results of our modeling
provide insight into the chemical processes of the propargyl radical in dark
molecular clouds and highlight the importance of resonance-stabilized radicals
in PAH formation.Comment: 31 pages and 17 figures (including the appendix), accepted for
publication in The Astrophysical Journa
Detection of Two Interstellar Polycyclic Aromatic Hydrocarbons via Spectral Matched Filtering
Ubiquitous unidentified infrared emission bands are seen in many astronomical
sources. Although these bands are widely, if not unanimously, attributed to the
collective emission from polycyclic aromatic hydrocarbons, no single species
from this class has been detected in space. We present the discovery of two -CN
functionalized polycyclic aromatic hydrocarbons, 1- and 2-cyanonaphthalene, in
the interstellar medium aided by spectral matched filtering. Using radio
observations with the Green Bank Telescope, we observe both bi-cyclic ring
molecules in the molecular cloud TMC-1. We discuss potential in situ gas-phase
formation pathways from smaller organic precursor molecules
PDRs4All III: JWST's NIR spectroscopic view of the Orion Bar
(Abridged) We investigate the impact of radiative feedback from massive stars
on their natal cloud and focus on the transition from the HII region to the
atomic PDR (crossing the ionisation front (IF)), and the subsequent transition
to the molecular PDR (crossing the dissociation front (DF)). We use
high-resolution near-IR integral field spectroscopic data from NIRSpec on JWST
to observe the Orion Bar PDR as part of the PDRs4All JWST Early Release Science
Program. The NIRSpec data reveal a forest of lines including, but not limited
to, HeI, HI, and CI recombination lines, ionic lines, OI and NI fluorescence
lines, Aromatic Infrared Bands (AIBs including aromatic CH, aliphatic CH, and
their CD counterparts), CO2 ice, pure rotational and ro-vibrational lines from
H2, and ro-vibrational lines HD, CO, and CH+, most of them detected for the
first time towards a PDR. Their spatial distribution resolves the H and He
ionisation structure in the Huygens region, gives insight into the geometry of
the Bar, and confirms the large-scale stratification of PDRs. We observe
numerous smaller scale structures whose typical size decreases with distance
from Ori C and IR lines from CI, if solely arising from radiative recombination
and cascade, reveal very high gas temperatures consistent with the hot
irradiated surface of small-scale dense clumps deep inside the PDR. The H2
lines reveal multiple, prominent filaments which exhibit different
characteristics. This leaves the impression of a "terraced" transition from the
predominantly atomic surface region to the CO-rich molecular zone deeper in.
This study showcases the discovery space created by JWST to further our
understanding of the impact radiation from young stars has on their natal
molecular cloud and proto-planetary disk, which touches on star- and planet
formation as well as galaxy evolution.Comment: 52 pages, 30 figures, submitted to A&
PDRs4All IV. An embarrassment of riches: Aromatic infrared bands in the Orion Bar
(Abridged) Mid-infrared observations of photodissociation regions (PDRs) are
dominated by strong emission features called aromatic infrared bands (AIBs).
The most prominent AIBs are found at 3.3, 6.2, 7.7, 8.6, and 11.2 m. The
most sensitive, highest-resolution infrared spectral imaging data ever taken of
the prototypical PDR, the Orion Bar, have been captured by JWST. We provide an
inventory of the AIBs found in the Orion Bar, along with mid-IR template
spectra from five distinct regions in the Bar: the molecular PDR, the atomic
PDR, and the HII region. We use JWST NIRSpec IFU and MIRI MRS observations of
the Orion Bar from the JWST Early Release Science Program, PDRs4All (ID: 1288).
We extract five template spectra to represent the morphology and environment of
the Orion Bar PDR. The superb sensitivity and the spectral and spatial
resolution of these JWST observations reveal many details of the AIB emission
and enable an improved characterization of their detailed profile shapes and
sub-components. While the spectra are dominated by the well-known AIBs at 3.3,
6.2, 7.7, 8.6, 11.2, and 12.7 m, a wealth of weaker features and
sub-components are present. We report trends in the widths and relative
strengths of AIBs across the five template spectra. These trends yield valuable
insight into the photochemical evolution of PAHs, such as the evolution
responsible for the shift of 11.2 m AIB emission from class B in
the molecular PDR to class A in the PDR surface layers. This
photochemical evolution is driven by the increased importance of FUV processing
in the PDR surface layers, resulting in a "weeding out" of the weakest links of
the PAH family in these layers. For now, these JWST observations are consistent
with a model in which the underlying PAH family is composed of a few species:
the so-called 'grandPAHs'.Comment: 25 pages, 10 figures, to appear in A&
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