arXiv subjects

Alexander G. G. M. Tielens

Publications and source records attributed to Alexander G. G. M. Tielens.

At least 55 records · Page 3Linked to original sources

arXiv2019

Probing planet formation and disk substructures in the inner disk of Herbig Ae stars with CO rovibrational emission

[abridged]CO rovibrational lines are efficient probes of warm molecular gas and can give unique insights into the inner 10 AU of proto-planetary disks. Recent studies have found a relation between the ratio of lines originating from the second and first vibrationally excited state, denoted as $v2/v1$, and the emitting radius of CO. In disks around Herbig Ae stars the vibrational excitation is low when CO lines come from close to the star, and high when lines only probe gas at large radii (more than 5 AU). We aim to find explanations for the observed trends between CO vibrational ratio, emitting radii, and NIR excess, and identify their implications in terms of the physical and chemical structure of inner disks around Herbig stars. Slab models and full disk thermo chemical models are calculated. Simulated observations from the models are directly compared to the data. Broad CO lines with low vibrational ratios are best explained by a warm (400-1300 K) inner disk surface with gas-to-dust ratios below 1000; no CO is detected within/at the inner dust rim, due to dissociation at high temperatures. In contrast, explaining the narrow lines with high vibrational ratios requires an inner cavity of a least 5 AU in both dust and gas, followed by a cool (100-300 K) molecular gas reservoir with gas-to-dust ratios greater than 10000 at the cavity wall. In all cases the CO gas must be close to thermalization with the dust. The high gas-to-dust ratios needed to explain high $v2/v1$ in narrow CO lines for a subset of group I disks can naturally be interpreted as due to the dust traps that have been proposed to explain millimeter dust cavities. The broad lines seen in most group II objects indicate a very flat disk in addition to inner disk substructures within 10 AU that can be related to the substructures recently observed with ALMA.

astro-ph.EP↗

arXiv2019

Laboratory photo-chemistry of covalently bonded fluorene clusters: observation of an interesting PAH bowl-forming mechanism

The fullerene C$_{60}$, one of the largest molecules identified in the interstellar medium (ISM), has been proposed to form top-down through the photo-chemical processing of large (more than 60 C-atoms) polycyclic aromatic hydrocarbon (PAH) molecules. In this article, we focus on the opposite process, investigating the possibility that fullerenes form from small PAHs, in which bowl-forming plays a central role. We combine laboratory experiments and quantum chemical calculations to study the formation of larger PAHs from charged fluorene clusters. The experiments show that with visible laser irradiation, the fluorene dimer cation - [C$_{13}$H$_{9}$$-$C$_{13}$H$_{9}$]$^+$ - and the fluorene trimer cation - [C$_{13}$H$_{9}$$-$C$_{13}$H$_{8}$$-$C$_{13}$H$_{9}$]$^+$ - undergo photo-dehydrogenation and photo-isomerization resulting in bowl structured aromatic cluster-ions, C$_{26}$H$_{12}$$^+$ and C$_{39}$H$_{20}$$^+$, respectively. To study the details of this chemical process, we employ quantum chemistry that allows us to determine the structures of the newly formed cluster-ions, to calculate the hydrogen loss dissociation energies, and to derive the underlying reaction pathways. These results demonstrate that smaller PAH clusters (with less than 60 C-atoms) can convert to larger bowled geometries that might act as building blocks for fullerenes, as the bowl-forming mechanism greatly facilitates the conversion from dehydrogenated PAHs to cages. Moreover, the bowl-forming induces a permanent dipole moment that - in principle - allows to search for such species using radio astronomy.

astro-ph.IM↗

arXiv2018

High-Resolution SOFIA/EXES Spectroscopy of $\mathrm{SO}_2$ Gas in the Massive Young Stellar Object MonR2 IRS3: Implications for the Sulfur Budget

Sulfur has been observed to be severely depleted in dense clouds leading to uncertainty in the molecules that contain it and the chemistry behind their evolution. Here, we aim to shed light on the sulfur chemistry in young stellar objects (YSOs) by using high-resolution infrared spectroscopy of absorption by the $ν_3$ rovibrational band of SO$_2$ obtained with the Echelon-Cross-Echelle Spectrograph on the Stratospheric Observatory for Infrared Astronomy. Using local thermodynamic equilibrium models we derive physical parameters for the SO$_2$ gas in the massive YSO MonR2 IRS3. This yields a SO$_2$/$\mathrm{H}$ abundance lower limit of $5.6\pm0.5\times10^{-7}$, or $>\!4\%$ of the cosmic sulfur budget, and an intrinsic line width (Doppler parameter) of $b<3.20\;\mathrm{km\;s}^{-1}$. The small line widths and high temperature ($T_\mathrm{ex}=234\pm15\;\mathrm{K}$) locate the gas in a relatively quiescent region near the YSO, presumably in the hot core where ices have evaporated. This sublimation unlocks a volatile sulfur reservoir (e.g., sulfur allotropes as detected abundantly in comet 67P/Churyumov--Gerasimenko), which is followed by SO$_2$ formation by warm, dense gas-phase chemistry. The narrowness of the lines makes formation of SO$_2$ from sulfur sputtered off grains in shocks less likely toward MonR2 IRS3.

astro-ph.SR↗

arXiv2018

Infrared Detection of Abundant CS in the Hot Core AFGL 2591 at High Spectral Resolution with SOFIA/EXES

We have performed a 5-8 $μ$m spectral line survey of the hot molecular core associated with the massive protostar AFGL 2591, using the Echelon-Cross-Echelle Spectrograph (EXES) on the Stratospheric Observatory for Infrared Astronomy (SOFIA). We have supplemented these data with a ground based study in the atmospheric M band around 4.5 $μ$m using the iSHELL instrument on the Infrared Telescope Facility (IRTF), and the full N band window from 8-13 $μ$m using the Texas Echelon Cross Echelle Spectrograph (TEXES) on the IRTF. Here we present the first detection of ro-vibrational transitions of CS in this source. The absorption lines are centred on average around -10 kms$^{-1}$ and the line widths of CS compare well with the hot component of $^{13}$CO (around 10 kms$^{-1}$). Temperatures for CS, hot $^{13}$CO and $^{12}$CO v=1-2 agree well and are around 700 K. We derive a CS abundance of 8$\times$10$^{-3}$ and 2$\times$10$^{-6}$ with respect to CO and H$_2$ respectively. This enhanced CS abundance with respect to the surrounding cloud (1$\times$10$^{-8}$) may reflect sublimation of H$_2$S ice followed by gas-phase reactions to form CS. Transitions are in LTE and we derive a density of $>$10$^7$ cm$^{-3}$, which corresponds to an absorbing region of $<$0.04$''$. EXES observations of CS are likely to probe deeply into the hot core, to the base of the outflow. Submillimeter and infrared observations trace different components of the hot core as revealed by the difference in systemic velocities, line widths and temperatures, as well as the CS abundance.

astro-ph.GA↗

arXiv2018

Fully anharmonic infrared cascade spectra of polycyclic aromatic hydrocarbons

The infrared (IR) emission of polycyclic aromatic hydrocarbons (PAHs) permeates our universe; astronomers have detected the IR signatures of PAHs around many interstellar objects. The IR emission of interstellar PAHs differs from their emission as seen under conditions on Earth, as they emit through a collisionless cascade down through their excited vibrational states from high internal energies. The difficulty in reproducing interstellar conditions in the laboratory results in a reliance on theoretical techniques. However, the size and complexity of PAHs requires careful consideration when producing the theoretical spectra. In this work we outline the theoretical methods necessary to lead to a fully theoretical IR cascade spectra of PAHs including: an anharmonic second order vibrational perturbation theory (VPT2) treatment; the inclusion of Fermi resonances through polyads; and the calculation of anharmonic temperature band shifts and broadenings (including resonances) through a Wang--Landau approach. We also suggest a simplified scheme to calculate vibrational emission spectra that retains the essential characteristics of the full IR cascade treatment and can directly transform low temperature absorption spectra in IR cascade spectra. Additionally we show that past astronomical models were in error in assuming a 15 cm$^{-1}$ correction was needed to account for anharmonic emission effects.

astro-ph.GA↗

arXiv2018

From planes to bowls: photodissociation of the bisanthenequinone cation

We present a combined experimental and theoretical study of the photodissociation of the bisanthenequinone (C28H12O2) cation, Bq+. The experiments show that, upon photolysis, the Bq+ cation does not dehydrogenate, but instead fragments through the sequential loss of the two neutral carbonyl groups, causing the formation of five-membered carbon cycles. Quantum chemical calculations confirm this Bq+ -> [Bq - CO]+ -> [Bq - 2CO]+ sequence as the energetically most favorable reaction pathway. For the first CO loss, a transition state with a barrier of ~3.2 eV is found, substantially lower than the lowest calculated H loss dissociation pathway (~ 4.9 eV). A similar situation applies for the second CO loss channel (~3.8 eV vs. ~4.7 eV), but where the first dissociation step does not strongly alter the planar PAH geometry, the second step transforms the molecule into a bowl-shaped one.

physics.atm-clus↗

arXiv2018

Anharmonicity and the infrared emission spectrum of highly excited PAHs

Aims. Infrared (IR) spectroscopy is a powerful tool to study molecules in space. A key issue in such analyses is understanding the effect that temperature and anharmonicity have on different vibrational bands, and thus interpreting the IR spectra for molecules under various conditions. Methods. We combined second order vibrational perturbation theory and the Wang-Landau random walk technique to produce accurate IR spectra of highly excited PAHs. We fully incorporated anharmonic effects, such as resonances, overtones, combination bands, and temperature effects. Results. The results are validated against experimental results for the pyrene molecule (C16H10). In terms of positions, widths, and relative intensities of the vibrational bands, our calculated spectra are in excellent agreement with gas-phase experimental data.

astro-ph.IM↗

arXiv2018

Laboratory photo-chemistry of pyrene clusters: an efficient way to form large PAHs

In this work, we study the photodissociation processes of small PAH clusters (e.g., pyrene clusters). The experiments are carried out using a quadrupole ion trap in combination with time-of-flight (QIT-TOF) mass spectrometry. The results show that pyrene clusters are converted into larger PAHs under the influence of a strong radiation field. Specifically, pyrene dimer cations (e.g., [C$_{16}$H$_{10}$$-$C$_{16}$H$_{9}$]$^+$ or C$_{32}$H$_{19}$$^+$), will photo-dehydrogenate and photo-isomerize to fully aromatic cations (PAHs) (e.g., C$_{32}$H$_{16}$$^+$) with laser irradiation. The structure of new formed PAHs and the dissociation energy for these reaction pathways are investigated with quantum chemical calculations. These studies provide a novel efficient evolution routes for the formation of large PAHs in the interstellar medium (ISM) in a bottom-up process that will counteract the top-down conversion of large PAHs into rings and chains, and provide a reservoir of large PAHs that can be converted into C$_{60}$ and other fullerenes and large carbon cages.

astro-ph.IM↗

arXiv2018

Infrared Spectra of Hexa-peri-hexabenzocoronene Cations:HBC+ and HBC2+

We present the first infrared (IR) gas phase spectrum of a large and astronomically relevant PAH cation (C$_{42}$H$_{18}$$^+$, HBC$^+$) and its di-cation (C$_{42}$H$_{18}$$^{2+}$, HBC$^{2+}$). The spectra are recorded via infrared multi-photon dissociation (IRMPD) spectroscopy of ions stored in a quadrupole ion trap, using the intense infrared radiation of a free electron laser in the 530$-$1800 cm$^{-1}$ (5.6$-$18.9 $μ$m) range. HBC$^{+}$ shows main intense absorption peaks at 762 (13.12), 1060 (9.43), 1192 (8.39), 1280 (7.81), 1379 (7.25) and 1530 (6.54) cm$^{-1}$($μ$m), in good agreement with DFT calculations that after scaling to take the anharmonicities effect into account. HBC$^{2+}$ has its main absorption peaks at 660 (15.15), 766 (13.05), 1054 (9.49), 1176 (8.50), 1290 (7.75), 1370 (7.30) and 1530 (6.54) cm$^{-1}$($μ$m). Given the similarity in the cationic and di-cationic spectra, we have not identified an obvious diagnostic signature to the presence of multiply charged PAHs in space. While experimental issues associated with the IRMPD technique preclude a detailed comparison with interstellar spectra, we do note that the strong bands of HBC$^+$ and HBC$^{2+}$ at $\sim$ 6.5, 7.7, 8.4 and 13.1 $μ$m coincide with prominent aromatic infrared bands (AIBs). HBC has only trio CH groups and the out-of-plane CH bending mode of both HBC cations is measured at 13.1 $μ$m, squarely in the range predicted by theory and previously found in studies of small (substituted) PAHs. This study therefore supports the use of AIBs observed in the 11$-$14 $μ$m range as a diagnostic tool for the edge topology of large PAHs in space.

astro-ph.IM↗

arXiv2018

Laboratory gas-phase infrared spectra of two astronomically relevant PAH cations: diindenoperylene, C$_{32}$H$_{16}$$^+$ and dicoronylene, C$_{48}$H$_{20}$$^+$

The first gas-phase infrared spectra of two isolated astronomically relevant and large PAH cations - diindenoperylene (DIP) and dicoronylene (DC) - in the 530$-$1800 cm$^{-1}$ (18.9$-$5.6 $μ$m) range - are presented. Vibrational band positions are determined for comparison to the aromatic infrared bands (AIBs). The spectra are obtained via infrared multiphoton dissociation (IRMPD) spectroscopy of ions stored in a quadrupole ion trap (QIT) using the intense and tunable radiation of the free electron laser for infrared experiments (FELIX). DIP$^{+}$ shows its main absorption peaks at 737 (13.57), 800 (12.50), 1001 (9.99), 1070 (9.35), 1115 (8.97), 1152 (8.68), 1278 (7.83), 1420 (7.04) and 1550 (6.45) cm$^{-1}$($μ$m), in good agreement with DFT calculations that are uniformly scaled to take anharmonicities into account. DC$^+$ has its main absorption peaks at 853 (11.72), 876 (11.42), 1032 (9.69), 1168 (8.56), 1300 (7.69), 1427 (7.01) and 1566 (6.39) cm$^{-1}$($μ$m), that also agree well with the scaled DFT results presented here. The DIP$^+$ and DC$^+$ spectra are compared with the prominent infrared features observed towards NGC 7023. This results both in matches and clear deviations. Moreover, in the 11.0$-$14.0 $μ$m region, specific bands can be linked to CH out-of-plane (oop) bending modes of different CH edge structures in large PAHs. The molecular origin of these findings and their astronomical relevance are discussed.

astro-ph.IM↗

arXiv2018

Mapping low frequency carbon radio recombination lines towards Cassiopeia A at 340, 148, 54 and 43 MHz

Quantitative understanding of the interstellar medium requires knowledge of its physical conditions. Low frequency carbon radio recombination lines (CRRLs) trace cold interstellar gas, and can be used to determine its physical conditions (e.g., electron temperature and density). In this work we present spatially resolved observations of the low frequency ($\leq390$ MHz) CRRLs centered around C$268α$, C$357α$, C$494α$ and C$539α$ towards Cassiopeia A on scales of $\leq1.2$ pc. We compare the spatial distribution of CRRLs with other ISM tracers. This comparison reveals a spatial offset between the peak of the CRRLs and other tracers, which is very characteristic for photodissociation regions and that we take as evidence for CRRLs being preferentially detected from the surfaces of molecular clouds. Using the CRRLs we constrain the gas electron temperature and density. These constraints on the gas conditions suggest variations of less than a factor of two in pressure over $\sim1$ pc scales, and an average hydrogen density of $200$-$470$ cm$^{-3}$. From the electron temperature and density maps we also constrain the ionized carbon emission measure, column density and path length. Based on these, the hydrogen column density is larger than $10^{22}$ cm$^{-2}$, with a peak of $\sim4\times10^{22}$ cm$^{-2}$ towards the South of Cassiopeia A. Towards the southern peak the line of sight length is $\sim40$ pc over a $\sim2$ pc wide structure, which implies that the gas is a thin surface layer on a large (molecular) cloud that is only partially intersected by Cassiopeia A. These observations highlight the utility of CRRLs as tracers of low density extended HI and CO-dark gas halo's around molecular clouds.

astro-ph.GA↗

arXiv2017

Efficiency of radial transport of ices in protoplanetary disks probed with infrared observations: the case of CO$_2$

The efficiency of radial transport of icy solid material from outer disk to the inner disk is currently unconstrained. Efficient radial transport of icy dust grains could significantly alter the composition of the gas in the inner disk. Our aim is to model the gaseous CO$_2$ abundance in the inner disk and use this to probe the efficiency of icy dust transport in a viscous disk. Features in the simulated CO$_2$ spectra are investigated for their dust flux tracing potential. We have developed a 1D viscous disk model that includes gas and grain motions as well as dust growth, sublimation and freeze-out and a parametrisation of the CO$_2$ chemistry. The thermo-chemical code DALI was used to model the mid-infrared spectrum of CO$_2$, as can be observed with JWST-MIRI. CO$_2$ ice sublimating at the iceline increases the gaseous CO$_2$ abundance to levels equal to the CO$_2$ ice abundance of $\sim 10^{-5}$, which is three orders of magnitude more than the gaseous CO$_2$ abundances of $\sim 10^{-8}$ observed by Spitzer. Grain growth and radial drift further increase the gaseous CO$_2$ abundance. A CO$_2$ destruction rate of at least $10^{-11}$ s$^{-1}$ is needed to reconcile model prediction with observations. This rate is at least two orders of magnitude higher than the fastest known chemical destruction rate. A range of potential physical mechanisms to explain the low observed CO$_2$ abundances are discussed. Transport processes in disks can have profound effects on the abundances of species in the inner disk. The discrepancy between our model and observations either suggests frequent shocks in the inner 10 AU that destroy CO$_2$, or that the abundant midplane CO$_2$ is hidden from our view by an optically thick column of low abundance CO$_2$ in to the disk surface XDR/PDR. Other molecules, such as CH$_4$ or NH$_3$, can give further handles on the rate of mass transport.

astro-ph.EP↗

arXiv2017

The PAH emission characteristics of the reflection nebula NGC2023

We present 5-20 micron spectral maps of the reflection nebula NGC2023 obtained with the Infrared Spectrograph SL and SH modes on board the Spitzer Space Telescope which reveal emission from polycyclic aromatic hydrocarbons (PAHs), C60, and H2 superposed on a dust continuum. We show that several PAH emission bands correlate with each other and exhibit distinct spatial distributions revealing a spatial sequence with distance from the illuminating star. We explore the distinct morphology of the 6.2, 7.7 and 8.6 micron PAH bands and find that at least two spatially distinct components contribute to the 7--9 micron PAH emission in NGC2023. We report that the PAH features behave independently of the underlying plateaus. We present spectra of compact oval PAHs ranging in size from C_66 to C_210, determined computationally using density functional theory, and investigate trends in the band positions and relative intensities as a function of PAH size, charge and geometry. Based on the NASA Ames PAH database, we discuss the 7--9 micron components in terms of band assignments and relative intensities. We assign the plateau emission to very small grains with possible contributions from PAH clusters and identify components in the 7--9 micron emission that likely originates in these structures. Based on the assignments and the observed spatial sequence, we discuss the photochemical evolution of the interstellar PAH family as they are more and more exposed to the radiation field of the central star in the evaporative flows associated with the PDRs in NGC2023.

astro-ph.GA↗

arXiv2016

Observational Evidence Linking Interstellar UV Absorption to PAH Molecules

The 2175 Å UV extinction feature was discovered in the mid-1960s, yet its physical origin remains poorly understood. One suggestion is absorption by Polycyclic Aromatic Hydrocarbons (PAH) molecules, which is supported by theoretical molecular structure computations and by laboratory experiments. PAHs are positively detected by their 3.3, 6.2, 7.7 8.6, 11.3 & 12.7 $μ$m IR emission bands, which are specified by their modes of vibration. A definitive empirical link between the 2175 Å UV extinction, and the PAH IR emission bands, however, is still missing. We present a new sample of hot stars that have both 2175 Å absorption and PAH IR emission. We find significant shifts of the central wavelength of the UV absorption feature, up to 2350 Å, but predominantly in stars that also have IR PAH emission. These UV shifts depend on stellar temperature in a fashion that is similar to the shifts of the 6.2 and 7.7$μ$m PAH IR bands, namely the features are increasingly more red-shifted as the stellar temperature decreases, but only below $\sim 15$ kK. Above 15 kK both UV and IR features retain their nominal values. Moreover, we find a suggestive correlation between the UV and IR shifts. We hypothesize that these similar dependences of both the UV and IR features on stellar temperature hint to a common origin of the two in PAH molecules and may establish the missing link between the UV and IR observations. We further suggest that the shifts depend on molecular size, and that the critical temperature of $\sim 15$ kK above which no shifts are observed is related to the onset of UV driven hot-star winds and their associated shocks.

astro-ph.GA↗

arXiv2016

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons in the 3 μm region: Role of periphery

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau.

astro-ph.GA↗

arXiv2016

Kompaneets Model Fitting of the Orion-Eridanus Superbubble II: Thinking Outside of Barnard's Loop

The Orion star-forming region is the nearest active high-mass star-forming region and has created a large superbubble, the Orion-Eridanus superbubble. Recent work by Ochsendorf et al. has extended the accepted boundary of the superbubble. We fit Kompaneets models of superbubbles expanding in exponential atmospheres to the new, larger shape of the Orion-Eridanus superbubble. We find that this larger morphology of the superbubble is consistent with the evolution of the superbubble being primarily controlled by expansion into the exponential Galactic disk ISM if the superbubble is oriented with the Eridanus side farther from the Sun than the Orion side. Unlike previous Kompaneets model fits that required abnormally small scale heights for the Galactic disk (<40 pc), we find morphologically consistent models with scale heights of 80 pc, similar to that expected for the Galactic disk.

astro-ph.GA↗

arXiv2015

A panoptic model for planetesimal formation and pebble delivery

The journey from dust particle to planetesimal involves physical processes acting on scales ranging from micrometers (the sticking and restructuring of aggregates) to hundreds of astronomical units (the size of the turbulent protoplanetary nebula). Considering these processes simultaneously is essential when studying planetesimal formation. We develop a novel, global, semi-analytical model for the evolution of the mass-dominating dust particles in a turbulent protoplanetary disk that takes into account the evolution of the dust surface density while preserving the essential characteristics of the porous coagulation process. This panoptic model is used to study the growth from submicron to planetesimal sizes in disks around Sun-like stars. For highly porous ices, unaffected by collisional fragmentation and erosion, rapid growth to planetesimal sizes is possible in a zone stretching out to ${\sim}10\mathrm{~AU}$ for massive disks. When porous coagulation is limited by erosive collisions, the formation of planetesimals through direct coagulation is not possible, but the creation of a large population of aggregates with Stokes numbers close to unity might trigger the streaming instability (SI). However, we find that reaching conditions necessary for SI is difficult and limited to dust-rich disks, (very) cold disks, or disks with weak turbulence. Behind the snow-line, porosity-driven aggregation of icy grains results in rapid (${\sim}10^{4}\mathrm{~yr}$) formation of planetesimals. If erosive collisions prevent this, SI might be triggered for specific disk conditions. The numerical approach introduced in this work is ideally suited for studying planetesimal formation and pebble delivery simultaneously and will help build a coherent picture of the start of the planet formation process.

astro-ph.SR↗

arXiv2015

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons: the realm of anharmonicity

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micron CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (~4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilises intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3 micron band are discussed.

astro-ph.GA↗