arXiv subjects

Vincent J. Esposito

Publications and source records attributed to Vincent J. Esposito.

8 recordsLinked to original sources

arXiv2026

Infrared Spectroscopy and Photochemistry of Aromatic Nitriles in Para-Hydrogen Matrices

Motivated by recent detections of several aromatic nitriles in Taurus Molecular Cloud-1, we report laboratory and theoretical investigations of the vibrational spectroscopy and photochemistry of singly and doubly cyano-substituted benzene in solid para-hydrogen matrices. We compare the photochemistry of cyanobenzene (benzonitrile) and three dicyanobenzene isomers initiated by excitations at 193 nm. In addition, we report the photochemistry of deuterated cyanobenzene (d$_5$-cyanobenzene), enabling us to determine the major products produced during the cyanobenzene photodissociation. The major products observed in the photolysis of all the nitriles are HCN and HNC, which are likely produced by hydrogen abstraction from para-H$_2$ by the CN radical. This indicates that the major photodissociation channel involves cleavage of the bond between the ring and the nitrile group, forming the phenyl (or cyanophenyl) radical + CN. We observe secondary photoproducts similar to those found during benzene photolysis. Our findings may aid the interpretation of recent JWST mid-infrared observations of aromatics in photodissociation regions.

astro-ph.SR↗

arXiv2026

Detection of C$_{60}$ Combination Bands in the Near-IR Spectrum of Tc 1

We report the detection of a set of new near-infrared emission features between 3.5 and 5.2 $μ$m in JWST/NIRSpec observations of Tc 1, the planetary nebula known for displaying the cleanest and most prominent mid-infrared cosmic fullerene spectrum. These broad features share the same spatial distribution as the well-known C$_{60}$ and C$_{70}$ mid-infrared emission bands, peaking in an asymmetric ring approximately 5-6" from the central star. Through comparison with new anharmonic quantum chemical calculations, we demonstrate that these features arise from C$_{60}$ combination bands, marking their first detection in an astrophysical environment. The total energy radiated in the combination bands amounts to ~17% of the total energy emitted from all C$_{60}$ modes, with direct implications for fullerene cooling models. These near-infrared combination bands offer a promising new window for identifying and studying the molecular astrophysics of C$_{60}$ in sources where mid-infrared spectra are more complex.

astro-ph.GA↗

arXiv2026

The Computed Microwave Spectrum of the Protonated Fullerene C60H+

The largest known molecule in space, C60 , has been detected in its neutral and cationic form through its vibrational, UV-driven fluorescence emission spectrum and its electronic absorption spectrum, respectively. The detection of several polycyclic aromatic hydrocarbon molecules through their pure rotation spectrum in cold, dense, molecular cloud cores suggests that C60 might be present in these environments as well. The low flux of UV pumping photons in molecular cloud cores and the absence of suitably bright background stars, make detection of C60 and its cation through the commonly used methods impractical. As C60 has no permanent dipole moment, its pure rotational transitions are forbidden and its presence must be inferred from the rotational transitions of C60 derivatives with permanent dipole moments. Here, we present a study of the predicted rotational spectrum of protonated C60 that has a sizeable permanent dipole moment. Protonation of C60 reduces the icosahedral symmetry to Cs and results in a dipole moment of about 3.8 Debye. The resulting C60H+ is a closed shell system

astro-ph.GA↗

arXiv2026

PDRs4All: XVIII. The evolution of the PAH ionisation and PAH size distribution across the Orion Bar

We investigate the evolution of the PAH population's charge state and size across key physical zones in the Orion Bar, which include the HII region, the atomic PDR (APDR), and three HI/H2 dissociation fronts (DF1, DF2, and DF3). Utilising the NASA Ames PAH Infrared Spectroscopic Database (PAHdb) and the pyPAHdb spectral modelling tool, we analysed the MIRI-MRS observations of the Orion Bar from the "PDRs4All" ERS Program. pyPAHdb modelling reveals the fractional contribution of the different PAH charge states and sizes to the total PAH emission across the Orion Bar. Cationic PAH emission peaks in the APDR region, where neutral PAHs have minimal contribution. Emission from neutral PAHs peaks in the HII region that consists of emission from a face-on PDR associated to the background OMC-1 molecular cloud, and in the molecular cloud regions past DF2. PAH anions are observed deep within the DF2 and DF3 zones. The average PAH size ranges between ~$60-74$ Nc. The modelling reveals regions of top-down PAH formation at the ionisation front, and bottom-up PAH formation within the molecular cloud region. The PAH ionisation parameter $γ$ ranges between ~$2-9 x 10^4$. Intensity ratios tracing PAH ionisation scale well with $γ$ in regions encompassing edge-on or face-on PDR emission, but their correlation weakens within the molecular cloud zone. Modelling of the $5-15$ $μ$m PAH spectrum with pyPAHdb achieves comprehensive characterization of the net contribution of neutral and cationic PAHs across different environments, whereas empirical PAH proxy intensity ratio tracers can be highly variable and unreliable outside regions dominated by PDR emission. The derived average PAH size in the different physical zones is consistent with a view of PAHs being more extensively subjected to ultraviolet processing closer to the ionisation front, and less affected within the molecular cloud.

astro-ph.GA↗

arXiv2025

SPHEREx: Aromatics, Aliphatics and PAH Size across the Iris Nebula

Observations by the SpectroPhotometer for the History of the Universe, Epoch of Reionization, and Ices Explorer (SPHEREx) are combined with Spitzer spectral map data to study the aromatic, aliphatic, and PAH size evolution across the northwest photo-dissociation region (PDR) of the Iris Nebula (NGC7023). The 3.3-3.4 $μ$m complex (I$_{3.3}$) and 11.2 $μ$m (I$_{11.2}$) PAH band strength are determined through direct integration. In addition, the former is decomposed into a 3.3 (I'$_{3.3}$) and 3.4 $μ$m (I'$_{3.4}$) sub-feature by fitting SPHEREx bandpass-integrated photometry using a modeled, highly sampled, multi-component spectrum. I$_{3.3}$, I$_{11.2}$, I'$_{3.3}$, and I'$_{3.4}$ all peak at the PDR. The NASA Ames PAH IR Spectroscopic Database is used to obtain the average number of carbon atoms ($\overline{\rm N_{C}}$) and small PAH fraction ($f_{\rm small}$) by fitting the isolated PAH component of the Spitzer segment; $70\lesssim\overline{N_{C}}\lesssim76$ and $0.24\lesssim\text{f}_{\rm small}\lesssim0.36$. I'$_{3.4}$/I'$_{3.4}$, I$_{11.2}$/I$_{3.3}$, $\overline{\rm N_{C}}$, and $f_{\rm small}$ all show a demarcation that matches the large-scale morphology of the region. For I'$_{3.3}$ and I'$_{3.4}$ this is reflected by two distinct trends when plotted against each other, one associated with the dense, the other with the diffuse medium; $[N_{\rm H,ali}/N_{\rm H,aro}]_{\rm dense}$ = 0.42$\pm$0.01 and $[N_{\rm H,ali}/N_{\rm H,aro}]_{\rm diffuse}$ = 0.10$\pm$0.01. $\overline{\rm N_{C}}$ and $f_{\rm small}$ are tentatively correlated with I$_{11.2}$/I$_{3.3}$ (R=0.54$\pm$0.05 and -0.45$\pm$0.05, respectively). A wider variety of large(r) extended interstellar medium objects is required to tighten the correlations, turn them into quantitative calibrators for PAH size, and pin down the discrepancy of correlations with I'$_{3.3}$ involved.

astro-ph.GA↗

arXiv2024

The High-Resolution Far- to Near-Infrared Anharmonic Absorption Spectra of Cyano-Substituted Polycyclic Aromatic Hydrocarbons from 300-6200 cm$^{-1}$

Cyano-substituted polycyclic aromatic hydrocarbons (CN-PAHs) may contribute to the emission detected in the 7 - 9 $μ$m (1430 - 1100 cm$^{-1}$) and 11 - 15 $μ$m (900 - 670 cm$^{-1}$) regions of astronomical IR spectra. Anharmonic quantum chemical computations of 17 CN-PAH isomers for 4 small PAHs and Benzene reveal strong, broad absorption features across the entire 300 - 6200 cm$^{-1}$ (33 - 1.6 $μ$m) frequency range. In particular, when a FWHM of 15 cm$^{-1}$ is applied, the composite CN-PAH spectrum is almost indistinguishable from the unsubstituted-PAH spectrum. At high resolution, however, the infrared absorption spectra reveal unique, identifiable features of CN-PAHs in the 700 - 950, 1100 - 1300, 2000 - 2500, and 3400 - 3600 cm$^{-1}$ ranges. The in-plane and out-of-plane CH bending vibrational frequencies of CN-PAHs are shifted when comparing isomers and to their unsubstituted counterparts, making their differentiation in mixed laboratory experiments possible. The overall aromatic CH stretch fundamental (2950 - 3200 cm$^{-1}$) and first overtone (5950 - 6200 cm$^{-1}$) regions are relatively unaffected by the cyano-substitution, with changes only to the breadth and intensity of the bands. Detailed spectroscopic data on the normal mode components of each state reported herein provide the means to directly assign future laboratory spectra and to guide direct IR observations of astronomical regions with, e.g., JWST.

astro-ph.GA↗

arXiv2024

The Infrared Absorption Spectrum of Phenylacetylene and its Deuterated Isotopologue in the Mid- to Far-IR

Anharmonicity strongly influences the absorption and emission spectra of polycyclic aromatic hydrocarbon (PAH) molecules. Here, IR-UV ion-dip spectroscopy experiments together with detailed anharmonic computations reveal the presence of fundamental, overtone, as well as 2- and 3-quanta combination band transitions in the far- and mid-infrared absorption spectrum of phenylacetylene and its singly deuterated isotopologue. Strong absorption features in the 400-900 cm$^{\rm -1}$ range originate from CH(D) in-plane and out-of-plane wags and bends, as well as bending motions including the C$\equiv$C and CH bonds of the acetylene substituent and the aromatic ring. For phenylacetylene, every absorption feature is assigned either directly or indirectly to a single or multiple vibrational mode(s). The measured spectrum is dense, broad, and structureless in many regions but well characterized by computations. Upon deuteration, large isotopic shifts are observed. At frequencies above 1500 cm$^{\rm -1}$ for d$_1$-phenylacetylene, a one-to-one match is seen when comparing computations and experiment with all features assigned to combination bands and overtones. The C$\equiv$C stretch observed in phenylacetylene is not observed in d$_1$-phenylacetylene due to a computed 40-fold drop in intensity. Overall, a careful treatment of anharmonicity that includes 2- and 3-quanta modes is found to be crucial to understand the rich details of the infrared spectrum of phenylacetylene. Based on these results, it can be expected that such an all-inclusive anharmonic treatment will also be key for unraveling the infrared spectra of PAHs in general.

astro-ph.GA↗

arXiv2024

Towards the IR Detection of Carbonic Acid: Absorption and Emission Spectra

With the recent radioastronomical detection of cis-trans-carbonic acid (H$_2$CO$_3$) in a molecular cloud toward the galactic center, the more stable but currently unobserved cis-cis conformer is shown here to have strong IR features. While the higher-energy cis-trans-carbonic acid was detected at millimeter and centimeter wavelengths, owing to its larger dipole moment, the vibrational structure of cis-cis-carbonic acid is more amenable to its observation at micron wavelengths. Even so, both conformers have relatively large IR intensities, and some of these fall in regions not dominated by polycyclic aromatic hydrocarbons. Water features may inhibit observation near the 2.75 $μ$m hydride stretches, but other vibrational fundamentals and even overtones in the 5.5 $μ$m to 6.0 $μ$m range may be discernible with JWST data. This work has employed high-level, accurately benchmarked quantum chemical anharmonic procedures to compute exceptionally accurate rotational spectroscopic data compared to experiment. Such performance implies that the IR absorption and even cascade emission spectral features computed in this work should be accurate and will provide the needed reference for observation of either carbonic acid conformer in various astronomical environments.

astro-ph.GA↗