arXiv subjects

A. Candian

Publications and source records attributed to A. Candian.

16 recordsLinked to original sources

arXiv2026

JWST MIRI-MRS observations of the Red Rectangle: AIB class transformation in the outer nebula

Aims: We characterize the mid-infrared spectrum of the outer regions of the Red Rectangle nebula to probe the carbonaceous dust and molecular content beyond the circumbinary disk. Methods: We present JWST MIRI-MRS observations of the SW whisker, extracted from three distinct environments: the biconical outflow, the whisker itself, and the shadow region outside the outflow. We compare these with an archival ISO-SWS observation of the inner nebula. Results: The JWST spectra display only classical AIB emission on a weak dust continuum, with no signatures of the oxygen-rich circumbinary disk mineralogy nor of the rich molecular emission seen at optical wavelengths. The AIBs are predominantly Class A - in marked contrast to the exclusively Class B profiles previously reported for the inner regions - with systematic differences between the outflow and shadow regions pointing to environmentally driven PAH processing.

astro-ph.GA↗

arXiv2024

Photofragmentation of Corannulene (C20H10) and Sumanene (C21H12) cations in gas phase and its Astrophysical implications

The aromatic infrared Bands (AIBs) dominate the mid-infrared spectra of many galactic and extragalactic sources. These AIBs are generally attributed to fluorescent emission from aromatic molecules. Unified efforts from experimentalists and theoreticians to assign these AIB features have recently gotten additional impetus with the launch of the James Webb Space Telescope (JWST) as the Mid-InfraRed Instrument (MIRI) delivers mid-IR spectrum with greatly increased sensitivity and spectral resolution. PAHs in space can exist in either neutral or ionic forms, absorb UV photons and undergo fragmentation, becoming a rich source of small hydrocarbons. This top-down mechanism of larger PAHs fragmenting into smaller species is of utmost importance in photo-dissociation regions (PDR) in space. In this work, we experimentally and theoretically investigate the photo-fragmentation pathways of two astronomically significant PAH cations - corannulene (C20H10) and sumanene (C21H12) that are structural motifs of fullerene C60, to understand their sequential fragmentation pathways. The photo-fragmentation experiments exhibit channels that are much different from planar PAHs. The breakdown of carbon skeleton is found to have different pathways for C20H10 and C21H12 because of the number and positioning of pentagon rings; yet the most abundant low mass cations produced by these two species are found to be similar. The low mass cations showcased in this work could be of interest for their astronomical detections. For completeness, the qualitative photo fragmentation behaviour of the dicationic corannulene and sumanene have also been experimented, but the potential energy surface of these dications are beyond the scope of this paper.

astro-ph.GA↗

arXiv2024

Laser-induced fragmentation of coronene cations

Polycyclic aromatic hydrocarbons are an important component of the interstellar medium of galaxies and photochemistry plays a key role in the evolution of these species in space. Here, we explore the photofragmentation behaviour of the coronene cation (C24H12+) using time of flight mass spectrometry. The experiments show photodissociation fragmentation channels including the formation of bare carbon clusters (Cn+) and hydrocarbon chains (CnHx+). The mass spectrum of coronene is dominated by peaks from C11+ and C7H+. Density functional theory was used to calculate relative energies, potential dissociation pathways, and possible structures for relevant species. We identify 6-6 to 5-7 ring isomerisation as a key step in the formation of both the bare carbon clusters and the hydrocarbon chains observed in this study. We present the dissociation mechanism outlined here as a potential formation route for C60 and other astrochemically relevant species.

astro-ph.GA↗

arXiv2023

PDRs4All VI: Probing the Photochemical Evolution of PAHs in the Orion Bar Using Machine Learning Techniques

[Abridged] JWST observations of the Orion Bar have shown the incredible richness of PAH bands and their variation on small scales. We aim to probe the photochemical evolution of PAHs across the key zones of the photodissociation region (PDR) that is the Orion Bar using unsupervised machine learning. We use NIRSpec and MIRI IFU data from the JWST ERS Program PDRs4All. We lever bisecting k-means clustering to generate detailed spatial maps of the spectral variability in several wavelength regions. We discuss the variations in the cluster profiles and connect them to the local physical conditions. We interpret these variations with respect to the key zones: the HII region, the atomic PDR zone, and the three dissociation fronts. The PAH emission exhibits spectral variation that depends strongly on spatial position in the PDR. We find the 8.6um band to behave differently than all other bands which vary systematically with one another. We find uniform variation in the 3.4-3.6um bands and 3.4/3.3 intensity ratio. We attribute the carrier of the 3.4-3.6um bands to a single side group attached to very similarly sized PAHs. Cluster profiles reveal a transition between characteristic profiles classes of the 11.2um feature from the atomic to the molecular PDR zone. We find the carriers of each of the profile classes to be independent, and reason the latter to be PAH clusters existing solely deep in the molecular PDR. Clustering also reveals a connection between the 11.2 and 6.2um bands; and that clusters generated from variation in the 10.9-11.63um region can be used to recover those in the 5.95-6.6um region. Clustering is a powerful tool for characterizing PAH variability on both spatial and spectral scales. For individual bands as well as global spectral behaviours, we find UV-processing to be the most important driver of the evolution of PAHs and their spectral signatures in the Orion Bar.

astro-ph.GA↗

arXiv2021

IR photofragmentation of the Phenyl Cation: Spectroscopy and Fragmentation Pathways

We present the gas-phase infrared spectra of the phenyl cation, phenylium, in its perprotio C$_6$H$_5^+$ and perdeutero C$_6$D$_5^+$ forms, in the 260-1925 cm$^{-1}$ (5.2-38 $μ$m) spectral range, and investigate the observed photofragmentation. The spectral and fragmentation data were obtained using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy within a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR MS) located inside the cavity of the free electron laser FELICE (Free Electron Laser for Intra-Cavity Experiments). The $^1$A$_1$ singlet nature of the phenylium ion is ascertained by comparison of the observed IR spectrum with DFT calculations, using both harmonic and anharmonic frequency calculations. To investigate the observed loss of predominantly [2C,nH] (n=2-4) fragments, we explored the potential energy surface (PES) to unravel possible isomerization and fragmentation reaction pathways. The lowest energy pathways toward fragmentation include direct H elimination, and a combination of facile ring-opening mechanisms ($\leq2.4$ eV), followed by elimination of H or CCH$_2$. Energetically, all H-loss channels found are more easily accessible than CCH$_2$-loss. Calculations of the vibrational density of states for the various intermediates show that at high internal energies, ring opening is the thermodynamically the most advantageous, eliminating direct H-loss as a competing process. The observed loss of primarily [2C,2H] can be explained through entropy calculations that show favored loss of [2C,2H] at higher internal energies.

physics.chem-ph↗

arXiv2020

Photolysis-induced scrambling of PAHs as a mechanism for deuterium storage

Aim. We investigate the role of PAHs as a sink for deuterium in the interstellar medium and study UV photolysis as a potential process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologues of D-enriched, protonated anthracene and phenanthrene ions was recorded in a FTICR mass spectrometer. IRMPD spectroscopy using FELIX provided the IR spectra that were compared to DFT vibrational spectra; reaction barriers and rates were also calculated and related to the product abundances. Results. The mass spectra for both UV and IRMPD photolysis show the loss of H from [D-C$_{14}$H$_{10}$]$^+$, whereas [H-C$_{14}$D$_{10}$]$^+$ shows a strong preference for D loss. Calculations reveal facile 1,2-H and -D shift reactions, with barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes in the 2 PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The $\sim$0.1 eV difference in zero-point energy between C-H and C-D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D. Conclusion. Scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to an aromatic site, protecting it from elimination. This could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C-HD group on solo sites might be responsible for the majority of aliphatic C-D stretching bands seen in astronomical spectra.

astro-ph.SR↗

arXiv2019

The aromatic Universe

The rich molecular structures of polycyclic aromatic hydrocarbons -- essentially planar flakes of fused benzene rings -- and their fullerene cousins are revealed through their vibrational and electronic spectra.

astro-ph.GA↗

arXiv2019

Anharmonicity in the mid-infrared spectra of polycyclic aromatic hydrocarbons: Molecular beam spectroscopy and calculations

Aims. In this work we determine the effects of anharmonicity on the mid-infrared spectra of the linear polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, tetracene and pentacene recorded using the free electron laser FELIX. Methods. Comparison of experimental spectra obtained under supersonic jet conditions with theoretically predicted spectra was used to show if anharmonicity explicitly needs to be taken into account. Results. Anharmonic spectra obtained using second-order vibrational perturbation theory agree on average within 0.5% of the experimental frequencies. Importantly, they confirm the presence of combination bands with appreciable intensity in the 5-6 $μ$m region. These combination bands contain a significant fraction of the IR absorption, which scales linearly with the size of the PAH. Detection and assignment of the combination bands are a preliminary indication of the accuracy of far-IR modes in our anharmonic theoretical spectra. Detailed analysis of the periphery-sensitive CH out-of-plane band of naphthalene reveals that there is still room for improvement of the VPT2 approach. In addition, the implications of our findings for the analysis of the aromatic infrared bands are discussed.

astro-ph.GA↗

arXiv2018

Photoinduced polycyclic aromatic hydrocarbon dehydrogenation: The competition between H- and H2-loss

PAHs constitute a major component of the interstellar medium carbon budget, locking up to 10--20% of the elemental carbon. Sequential fragmentation induced by energetic photons leads to the formation of new species, including fullerenes. However, the exact chemical routes involved in this process remain largely unexplored. In this work, we focus on the first photofragmentation steps, which involve the dehydrogenation of these molecules. For this, we consider a multidisciplinary approach, taking into account the results from experiments, DFT calculations, and modeling using dedicated Monte-Carlo simulations. By considering the simplest isomerization pathways --- i.e., hydrogen roaming along the edges of the molecule --- we are able to characterize the most likely photodissociation pathways for the molecules studied here. These comprise nine PAHs with clearly different structural properties. The formation of aliphatic-like side groups is found to be critical in the first fragmentation step and, furthermore, sets the balance of the competition between H- and H2-loss. We show that the presence of trio hydrogens, especially in combination with bay regions in small PAHs plays an important part in the experimentally established variations in the odd-to-even H-atom loss ratios. In addition, we find that, as PAH size increases, H2 formation becomes dominant, and sequential hydrogen loss only plays a marginal role. We also find disagreements between experiments and calculations for large, solo containing PAHs, which need to be accounted for. In order to match theoretical and experimental results, we have modified the energy barriers and restricted the H-hopping to tertiary atoms. The formation of H2 in large PAHs upon irradiation appears to be the dominant fragmentation channel, suggesting an efficient formation path for molecular hydrogen in PDRs.

astro-ph.GA↗

arXiv2018

Photoinduced polycyclic aromatic hydrocarbon dehydrogenation: Molecular hydrogen formation in dense PDRs

The physical and chemical conditions in photodissociation regions (PDRs) are largely determined by the influence of far ultraviolet radiation. Far-UV photons can efficiently dissociate molecular hydrogen, a process that must be balanced at the HI/H2 interface of the PDR. Given that reactions involving hydrogen atoms in the gas phase are highly inefficient under interstellar conditions, H2 formation models mostly rely on catalytic reactions on the surface of dust grains. Additionally, molecular hydrogen formation in polycyclic aromatic hydrocarbons (PAHs) through the Eley-Rideal mechanism has been considered as well, although it has been found to have low efficiency in PDR fronts. In a previous work, we have described the possibility of efficient H2 release from medium to large sized PAHs upon photodissociation, with the exact branching between H-/H2-loss reactions being molecule dependent. Here we investigate the astrophysical relevance of this process, by using a model for the photofragmentation of PAHs under interstellar conditions. We focus on three PAHs cations (coronene, ovalene and circumcoronene), which represent three possibilities in the branching of atomic and molecular hydrogen losses. We find that, for ovalene (H2-loss dominated) the rate coefficient for H2 formation reaches values of the same order as H2 formation in dust grains. This result suggests that this hitherto disregarded mechanism can account, at least partly, for the high level of molecular hydrogen formation in dense PDRs.

astro-ph.GA↗

arXiv2018

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons in the 3 micron region: role of hydrogenation and alkylation

Aims. We aim to elucidate the spectral changes in the 3 micron region that result from chemical changes in the molecular periphery of polycyclic aromatic hydrocarbons (PAHs) with extra hydrogens (H-PAHs) and methyl groups (Me-PAHs). Methods. Advanced laser spectroscopic techniques combined with mass spectrometry were applied on supersonically cooled 1,2,3,4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenathrene, 1,2,3,6,7,8-hexahydropyrene, 9-methylanthracene, and 9,10-dimethylanthracene, allowing us to record mass-selective and conformationally selective absorption spectra of the aromatic, aliphatic, and alkyl CH-stretches in the 3.175-3.636 micron region with laser-limited resolution. We compared the experimental absorption spectra with standard harmonic calculations and with second-order vibrational perturbation theory anharmonic calculations that use the SPECTRO program for treating resonances. Results. We show that anharmonicity plays an important if not dominant role, affecting not only aromatic, but also aliphatic and alkyl CH-stretch vibrations. The experimental high-resolution data lead to the conclusion that the variation in Me- and H-PAHs composition might well account for the observed variations in the 3 micron emission spectra of carbon-rich and star-forming regions. Our laboratory studies also suggest that heavily hydrogenated PAHs form a significant fraction of the carriers of IR emission in regions in which an anomalously strong 3 micron plateau is observed.

astro-ph.GA↗

arXiv2016

Mapping PAH sizes in NGC 7023 with SOFIA

NGC 7023 is a well-studied reflection nebula, which shows strong emission from polycyclic aromatic hydrocarbon (PAH) molecules in the form of aromatic infrared bands (AIBs). The spectral variations of the AIBs in this region are connected to the chemical evolution of the PAH molecules which, in turn, depends on the local physical conditions. We use the capabilities of SOFIA to observe a 3.2' x 3.4' region of NGC 7023 at wavelengths that we observe with high spatial resolution (2.7") at 3.3 and 11.2 um. We compare the SOFIA images with existing images of the PAH emission at 8.0 um (Spitzer), emission from evaporating very small grains (eVSG) extracted from Spitzer-IRS spectral cubes, the ERE (HST and CFHT), and H_2 (2.12 um). We create maps of the 11.2/3.3 um ratio to probe the morphology of the PAH size distribution and the 8.0/11.2 um ratio to probe the PAH ionization. We make use of an emission model and of vibrational spectra from the NASA Ames PAHdb to translate the 11.2/3.3 um ratio to PAH sizes. The 11.2/3.3 um map shows the smallest PAH concentrate on the PDR surface (H_2 and extended red emission) in the NW and South PDR. We estimated that PAHs in the NW PDR bear, on average, a number of carbon atoms (N_c) of ~70 in the PDR cavity and ~50 at the PDR surface. In the entire nebula, the results reveal a factor of 2 variation in the size of the PAH. We relate these size variations to several models for the evolution of the PAH families when they traverse from the molecular cloud to the PDR. The PAH size map enables us to follow the photochemical evolution of PAHs in NGC 7023. Small PAHs result from the photo-evaporation of VSGs as they reach the PDR surface. Inside the PDR cavity, the PAH abundance drops as the smallest PAH are broken down. The average PAH size increases in the cavity where only the largest species survive or are converted into C_60 by photochemical processing.

astro-ph.GA↗

arXiv2015

The 11.2 $μ$m emission of PAHs in astrophysical objects

The 11.2 $μ$m emission band belongs to the family of the `Unidentified' Infrared (UIR) emission bands seen in many astronomical environments. In this work we present a theoretical interpretation of the band characteristics and profile variation for a number of astrophysical sources in which the carriers are subject to a range of physical conditions. The results of Density Functional Theory (DFT) calculations for the solo out-of-plane (OOP) vibrational bending modes of large polycyclic aromatic hydrocarbon (PAH) molecules are used as input for a detailed emission model which includes the temperature and mass dependence of PAH band wavelength, and a PAH mass distribution that varies with object. Comparison of the model with astronomical spectra indicates that the 11.2 $μ$m band asymmetry and profile variation can be explained principally in terms of the mass distribution of neutral PAHs with a small contribution from anharmonic effects.

astro-ph.GA↗

arXiv2014

Polycyclic Aromatic Hydrocarbons with armchair edges and the 12.7 μm band

In this Letter we report the results of density functional theory calculations on medium-sized neutral Polycyclic Aromatic Hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 μm and in the fingerprint region (10-15 μm), and also strong ring deformation modes around 12.7 μm. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common - although generally weak. We then propose that armchair PAHs with NC >65 are responsible for the 12.7 μm Aromatic Infrared Band in HII regions and discuss astrophysical implications in the context of the PAH life-cycle.

astro-ph.GA↗

arXiv2013

Integral field spectroscopy of M1-67. A Wolf-Rayet nebula with LBVN appearance

This work aims to disentangle the morphological, kinematic, and chemical components of the nebula M1-67 to shed light on its process of formation around the central Wolf-Rayet (WR) star WR124. We have carried out integral field spectroscopy observations over two regions of M1-67, covering most of the nebula in the optical range. Maps of electron density, line ratios, and radial velocity were created to perform a detailed analysis of the two-dimensional structure. We studied the physical and chemical properties by means of integrated spectra selected over the whole nebula. Photoionization models were performed to confirm the empirical chemical results theoretically. In addition, we analysed infrared spectroscopic data and the MIPS 24micron image of M1-67 from Spitzer. We find that the ionized gas of M1-67 is condensed in knots aligned in a preferred axis along the NE-SW direction, like a bipolar structure. Both electron density and radial velocity decrease in this direction when moving away from the central star. From the derived electron temperature, Te~8200 K, we have estimated chemical abundances, obtaining that nitrogen appears strongly enriched and oxygen depleted. From the last two results, we infer that this bipolarity is the consequence of an ejection of an evolved stage of WR124 with material processed in the CNO cycle. The infrared study has revealed that the bipolar axis is composed of ionized gas with a low ionization degree that is well mixed with warm dust and of a spherical bubble surrounding the ejection at 24micron. Taking the evolution of a 60 Mo star and the temporal scale of the bipolar ejection into account, we propose that the observed gas was ejected during an eruption in the luminous blue variable. The star has entered the WR phase recently without apparent signs of interaction between WR-winds and interstellar material.

astro-ph.GA↗

arXiv2012

Spatial distribution and interpretation of the 3.3 \mum PAH emission band of the Red Rectangle

The spatial distribution of 3.3 \mum PAH and associated emission in the 3.3" x 6.0" inner region of the Red Rectangle nebula has been determined using the UIST imager-spectrometer at the United Kingdom Infrared Telescope (UKIRT). Interpretation of the 3.3 \mum feature as comprising two spectroscopic components centred at 3.30 \mum and 3.28 \mum, as put forward by Song et al. (2003, 2007), is supported by these data which reveal that they have different spatial distributions. It is deduced that there are two classes of 3.3 \mum band carrier with a peak wavelength separation of ~0.02 \mum. From comparison of the 3.3 \mum observations with laboratory and theoretical spectra for a range of PAH molecules it is proposed that the 3.28 \mum and 3.30 \mum components arise from 'bay' and 'non-bay' hydrogen sites, respectively, on the periphery of small neutral PAHs. Observational data are also obtained for L-band continuum emission and for the Pfund εhydrogen recombination line.

astro-ph.GA↗