arXiv subjects

Sandra Brünken

Publications and source records attributed to Sandra Brünken.

At least 19 recordsLinked to original sources

arXiv2026

First detection of C2H+ in the interstellar medium

Despite the detection of nearly 350 molecules in the interstellar medium, almost half of which are carbon chains, the pathways that build molecular complexity remain poorly understood. Observed abundances of carbon-chain and aromatic species are difficult to reconcile with existing top-down or bottom-up formation scenarios, due in part to limited observational constraints and incomplete theoretical understanding. In particular, small intermediary ions, key drivers of ion-molecule reactions capable of seeding larger hydrocarbons and aromatic rings, could provide critical support for the bottom-up formation scenario. Constraining the abundance and chemistry of these ions is therefore essential to test whether bottom-up growth can operate efficiently under interstellar conditions. Here, we report the first detection of the small hydrocarbon cation ethynylium, C2H+, toward the Orion Bar, based on observations with the APEX 12m sub-mm telescope of its lowest-lying J=3-2 rotational transition near 211GHz, which exhibits a unique spectroscopic fingerprint through resolved Lambda-doubling and hyperfine splitting components, as recently measured in the laboratory. Meudon PDR models successfully reproduce these values, placing C2H+ formation at the outer edges of PDR fronts. Our results link C2H+ production to CH+ and CH3+ within a network of ion-molecule reactions driven by vibrationally excited H2, a scenario now further supported by recent detections of these species in PDRs like the Orion Bar with JWST observations. The importance of C2H+ lies in its role as a key intermediate: it produces C2H2+ and subsequently C2H3+, effectively channelling small C2 building blocks toward larger hydrocarbons and facilitating bottom-up growth at the PDR surface. Targeted searches for C2H+ in other regions promise to provide a potentially decisive probe of ion-driven bottom-up chemistry in the ISM.

astro-ph.GA↗

arXiv2026

Oxygen in the protostellar clump OMC-2 FIR4

Atomic oxygen (OI), OH, H2O, and CO are the main carriers of oxygen in dense interstellar gas and important coolants of shocks associated with protostellar outflows. We determine the relative abundances of these species in the warm inner parts of the protostellar clump OMC-2 FIR4 in Orion A. The clump contains several young stellar objects. The upGREAT receiver including the High Frequency Array (HFA, operating at 4.74 THz, 63 micron) onboard the Stratospheric Observatory for Far-Infrared Astronomy (SOFIA) was used to observe OMC-2 FIR4 in the lines of OI, OH, OD, HDO, and CO. Additional HDO lines were observed with the Atacama Pathfinder Experiment (APEX). Archival H2O and CO spectra observed by the Herschel satellite were included in the analysis. The observed lines were reasonably well reproduced by an expanding spherical shell model. The OI spectrum at 63 micron towards OMC-2 FIR4 is dominated by a broad line component, on top of which medium-wide and narrow line components can be discerned. The same components are present in the OH, H2O, and high-J CO spectra towards this source. We find that OI is more abundant than H2O in the shocked gas. In the broad line component, the following abundance ratios are derived: OI/H2O ~ 700, OI/OH ~ 300, OI/CO ~ 4. The high relative abundance of atomic oxygen there suggests an origin in dissociative J-shocks that are associated with strong ultraviolet radiation. The OI/CO ratio decreases below unity in the components with a smaller velocity dispersion, and these components also have higher abundances of H2O than the broad line component, although remaining below that of CO. The HDO/H2O ratio in the low-velocity components corresponds to the average ratio in the icy mantles of dust grains, and the presence of water there could also be understood in terms of sublimation without invoking high-temperature chemistry.

astro-ph.GA↗

arXiv2026

High-resolution ro-vibrational and rotational spectroscopy of the open-shell, linear CCH$^+$ ion ($^3Π$)

In this work, we report on the high-resolution infrared spectrum of CCH$^+$ ($^3Π$) recorded in the range $3066-3184$~cm$^{-1}$ by means of leak-out spectroscopy. This spectral range covers the fundamental of the CH stretching mode and a highly excited bending vibrational mode. Based on this data (385 ro-vibrational lines), accurate spectroscopic descriptions of the ground and the two vibrationally excited states of CCH$^+$ were obtained. Besides the band origins, spin-orbit coupling constants, rotational constants, centrifugal distortion constants and $Λ$-doubling constants for the ground and excited vibrational states have been derived. This effective Hamiltonian analysis allowed a search for pure rotational lines of CCH$^+$ in its electronic and vibrational ground state using a two-color millimeterwave - infrared scheme. We observed all rotational transitions from $J^{\prime\prime} = 2$ up to $J^{\prime\prime} = 6$ within the $Ω= 2$ lowest energy fine structure component with resolved hyperfine splittings. This data has already guided the first detection of CCH$^+$ in space toward the Orion Bar photo-dissociation region, and has the potential to support further astronomical searches for CCH$^+$ either through radio or infrared spectroscopy, for example with the James Webb Space Telescope.

physics.chem-ph↗

arXiv2026

Experimental proof of strong $Π$-$Σ$ mixing in the Renner-Teller and Pseudo-Jahn-Teller affected CCH$^+$ ($^3Π$) ion

The ethynyl radical cation, CCH$^+$ ($^3Π$), offers a unique system for fundamental spectroscopic studies of non-adiabatic effects due to its open-shell linear structure and the presence of a low-lying $^3Σ^-$ state, which induces notable perturbations in the (ro-)vibrational spectrum. To probe these effects, we recorded the broadband vibrational spectrum of CCH$^+$ from 350-3450 cm$^{-1}$ using leak-out spectroscopy. The spectrum reveals a complex splitting pattern in the CCH bending mode, attributed to Renner-Teller and pseudo-Jahn-Teller coupling effects between the $^3 Π$ and $^3 Σ^-$ electronic states. A three-state diabatic model, validated here against high-resolution IR data of the CH stretching mode, facilitated assignments within the broadband infrared (IR) spectrum, including an additional $Π$ vibronic feature observed in the aforementioned high-resolution spectrum. Our results highlight a pronounced sensitivity of the splitting pattern to the $Π$-$Σ$ energy gap, with couplings so large that even the zero-point vibrational motion of the bending vibration is sufficient to disrupt the vibronic structure of this ion. This compact ion, with strong coupling effects and high-quality spectroscopic data, serves as an exemplary system for evaluating non-adiabatic models.

physics.chem-ph↗

arXiv2025

Infrared Spectroscopy of Pentagon-Containing PAHs: Indenyl and Fluorenyl Anions and Indenyl Cation

Polycyclic aromatic hydrocarbon (PAH) ions are crucial intermediates in interstellar chemistry and may play a key role in the infrared emission features observed in space. Here, we investigate the infrared spectra of the indenyl (C$_9$H$_7^-$) and fluorenyl (C$_{13}$H$_9^-$) anions and the indenyl cation (C$_9$H$_7^+$) using infrared pre-dissociation (IRPD) spectroscopy. The experiments were performed in a cryogenic 22 pole ion trap at the FELion beamline of the tunable free-electron laser FELIX. Spectral analysis of the two anionic PAHs, in combination with density functional theory (DFT) computations, revealed key vibrational modes near 1300 cm$^{-1}$, making these ions potential carriers of the 7.7 μm PAH emission band seen in many astronomical objects. The feature-rich spectrum of cationic indenyl could not be entirely explained by modeling through time-independent anharmonic DFT calculations. Although a better match has been achieved through molecular dynamics simulations, we cannot completely rule out the presence of multiple cationic isomers of the H-loss fragments of indene in the experiments.

astro-ph.GA↗

arXiv2024

PDRs4All VIII: Mid-IR emission line inventory of the Orion Bar

Mid-infrared emission features probe the properties of ionized gas, and hot or warm molecular gas. The Orion Bar is a frequently studied photodissociation region (PDR) containing large amounts of gas under these conditions, and was observed with the MIRI IFU aboard JWST as part of the "PDRs4All" program. The resulting IR spectroscopic images of high angular resolution (0.2") reveal a rich observational inventory of mid-IR emission lines, and spatially resolve the substructure of the PDR, with a mosaic cutting perpendicularly across the ionization front and three dissociation fronts. We extracted five spectra that represent the ionized, atomic, and molecular gas layers, and measured the most prominent gas emission lines. An initial analysis summarizes the physical conditions of the gas and the potential of these data. We identified around 100 lines, report an additional 18 lines that remain unidentified, and measured the line intensities and central wavelengths. The H I recombination lines originating from the ionized gas layer bordering the PDR, have intensity ratios that are well matched by emissivity coefficients from H recombination theory, but deviate up to 10% due contamination by He I lines. We report the observed emission lines of various ionization stages of Ne, P, S, Cl, Ar, Fe, and Ni, and show how certain line ratios vary between the five regions. We observe the pure-rotational H$_2$ lines in the vibrational ground state from 0-0 S(1) to 0-0 S(8), and in the first vibrationally excited state from 1-1 S(5) to 1-1 S(9). We derive H$_2$ excitation diagrams, and approximate the excitation with one thermal (~700 K) component representative of an average gas temperature, and one non-thermal component (~2700 K) probing the effect of UV pumping. We compare these results to an existing model for the Orion Bar PDR and highlight the differences with the observations.

astro-ph.GA↗

arXiv2024

A far-ultraviolet-driven photoevaporation flow observed in a protoplanetary disk

Most low-mass stars form in stellar clusters that also contain massive stars, which are sources of far-ultraviolet (FUV) radiation. Theoretical models predict that this FUV radiation produces photo-dissociation regions (PDRs) on the surfaces of protoplanetary disks around low-mass stars, impacting planet formation within the disks. We report JWST and Atacama Large Millimetere Array observations of a FUV-irradiated protoplanetary disk in the Orion Nebula. Emission lines are detected from the PDR; modelling their kinematics and excitation allows us to constrain the physical conditions within the gas. We quantify the mass-loss rate induced by the FUV irradiation, finding it is sufficient to remove gas from the disk in less than a million years. This is rapid enough to affect giant planet formation in the disk.

astro-ph.GA↗

arXiv2023

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 $μ$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 $μ$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 $μ$m AIB emission from class B$_{11.2}$ in the molecular PDR to class A$_{11.2}$ 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'.

astro-ph.GA↗

arXiv2023

PDRs4All II: JWST's NIR and MIR imaging view of the Orion Nebula

The JWST has captured the most detailed and sharpest infrared images ever taken of the inner region of the Orion Nebula, the nearest massive star formation region, and a prototypical highly irradiated dense photo-dissociation region (PDR). We investigate the fundamental interaction of far-ultraviolet photons with molecular clouds. The transitions across the ionization front (IF), dissociation front (DF), and the molecular cloud are studied at high-angular resolution. These transitions are relevant to understanding the effects of radiative feedback from massive stars and the dominant physical and chemical processes that lead to the IR emission that JWST will detect in many Galactic and extragalactic environments. Due to the proximity of the Orion Nebula and the unprecedented angular resolution of JWST, these data reveal that the molecular cloud borders are hyper structured at small angular scales of 0.1-1" (0.0002-0.002 pc or 40-400 au at 414 pc). A diverse set of features are observed such as ridges, waves, globules and photoevaporated protoplanetary disks. At the PDR atomic to molecular transition, several bright features are detected that are associated with the highly irradiated surroundings of the dense molecular condensations and embedded young star. Toward the Orion Bar PDR, a highly sculpted interface is detected with sharp edges and density increases near the IF and DF. This was predicted by previous modeling studies, but the fronts were unresolved in most tracers. A complex, structured, and folded DF surface was traced by the H2 lines. This dataset was used to revisit the commonly adopted 2D PDR structure of the Orion Bar. JWST provides us with a complete view of the PDR, all the way from the PDR edge to the substructured dense region, and this allowed us to determine, in detail, where the emission of the atomic and molecular lines, aromatic bands, and dust originate.

astro-ph.GA↗

arXiv2023

Infrared action spectroscopy as tool for probing gas-phase dynamics: Protonated Dimethyl Ether, (CH$_3$)$_2$OH$^+$, formed by the reaction of CH$_3$OH$_{2}^{+}$ with CH$_3$OH

Methanol is one of the most abundant interstellar Complex Organic Molecules (iCOMs) and it represents a major building block for the synthesis of increasingly complex oxygen-containing molecules. The reaction between protonated methanol and its neutral counterpart, giving protonated dimethyl ether, (CH$_3$)$_2$OH$^+$, along with the ejection of a water molecule, has been proposed as a key reaction in the synthesis of dimethyl ether in space. Here, gas phase vibrational spectra of the (CH$_3$)$_2$OH$^+$ reaction product and of the [C$_2$H$_9$O$_2$]$^+$ intermediate complex(es), formed under different pressure and temperature conditions, are presented. The widely tunable free electron laser for infrared experiments, FELIX, was employed to record their vibrational fingerprint spectra using different types of infrared action spectroscopy in the $600-1700$ cm$^{-1}$ frequency range, complemented with measurements using an OPO/OPA system to cover the O-H stretching region $3400-3700$ cm$^{-1}$. The formation of protonated dimethyl ether as a product of the reaction is spectroscopically confirmed, providing the first gas-phase vibrational spectrum of this potentially relevant astrochemical ion.

astro-ph.GA↗

arXiv2021

Infrared action spectroscopy of doubly charged PAHs and their contribution to the aromatic infrared bands

The so-called aromatic infrared bands are attributed to emission of polycyclic aromatic hydrocarbons. The observed variations toward different regions in space are believed to be caused by contributions of different classes of PAH molecules, i.e. with respect to their size, structure, and charge state. Laboratory spectra of members of these classes are needed to compare them to observations and to benchmark quantum-chemically computed spectra of these species. In this paper we present the experimental infrared spectra of three different PAH dications, naphthalene$^{2+}$, anthracene$^{2+}$, and phenanthrene$^{2+}$, in the vibrational fingerprint region 500-1700~cm$^{-1}$. The dications were produced by electron impact ionization of the vapors with 70 eV electrons, and they remained stable against dissociation and Coulomb explosion. The vibrational spectra were obtained by IR predissociation of the PAH$^{2+}$ complexed with neon in a 22-pole cryogenic ion trap setup coupled to a free-electron infrared laser at the Free-Electron Lasers for Infrared eXperiments (FELIX) Laboratory. We performed anharmonic density-functional theory calculations for both singly and doubly charged states of the three molecules. The experimental band positions showed excellent agreement with the calculated band positions of the singlet electronic ground state for all three doubly charged species, indicating its higher stability over the triplet state. The presence of several strong combination bands and additional weaker features in the recorded spectra, especially in the 10-15~$μ$m region of the mid-IR spectrum, required anharmonic calculations to understand their effects on the total integrated intensity for the different charge states. These measurements, in tandem with theoretical calculations, will help in the identification of this specific class of doubly-charged PAHs as carriers of AIBs.

astro-ph.GA↗

arXiv2020

Structural investigation of doubly-dehydrogenated pyrene cations

The vibrationally resolved spectra of the pyrene cation and doubly-dehydrogenated pyrene cation (C$_{16}$H$_{10}$$^{.+}$; Py$^+$ and C$_{16}$H$_{8}$$^{.+}$; ddPy$^+$) are presented. Infrared predissociation spectroscopy is employed to measure the vibrational spectrum of both species using a cryogenically cooled 22-pole ion trap. The spectrum of Py$^+$ allows a detailed comparison with harmonic and anharmonic density functional theory (DFT) calculated normal mode frequencies. The spectrum of ddPy$^+$ is dominated by absorption features from two isomers (4,5-ddPy$^+$ and 1,2-ddPy$^+$) with, at most, minor contributions from other isomers. These findings can be extended to explore the release of hydrogen from interstellar PAH species. Our results suggest that this process favours the loss of adjacent hydrogen atoms.

astro-ph.GA↗

arXiv2018

Direct Evidence of the Benzylium and Tropylium Cations as the two long-lived Isomers of C7H7+

Disentangling the isomeric structure of C7H7+ is a longstanding experimental issue. We report here the full mid-infrared vibrational spectrum of C7H7+ tagged with Ne obtained with infrared-predissociation spectroscopy at 10 K. Saturation depletion measurements were used to assign the contribution of benzylium and tropylium isomers and demonstrate that no other isomer is involved. Recorded spectral features compare well with density functional theory calculations. This opens perspectives for a better understanding and control of the formation paths leading to either tropylium or benzylium ions.

physics.chem-ph↗

arXiv2018

Identification of the fragment of the 1-methylpyrene cation by mid-IR spectroscopy

The fragment of the 1-methylpyrene cation, C17H11+, is expected to exist in two isomeric forms, 1-pyrenemethylium PyrCH2+ and the tropylium containing species PyrC7+ . We measured the infrared (IR) action spectrum of cold C17H11+ tagged with Ne using a cryogenic ion trap instrument coupled to the FELIX laser. Comparison of the experimental data with density functional theory calculations allows us to identify the PyrCH2+ isomer in our experiments. The IR Multi-Photon Dissociation spectrum was also recorded following the C2H2 loss channel. Its analysis suggests combined effects of anharmonicity and isomerisation while heating the trapped ions, as shown by molecular dynamics simulations.

physics.chem-ph↗

arXiv2017

Detection of interstellar ortho-D2H+ with SOFIA

We report on the detection of the ground-state rotational line of ortho-D2H+ at 1.477 THz (203 micron) using the German REceiver for Astronomy at Terahertz frequencies (GREAT) onboard the Stratospheric Observatory For Infrared Astronomy (SOFIA). The line is seen in absorption against far-infrared continuum from the protostellar binary IRAS 16293-2422 in Ophiuchus. The para-D2H+ line at 691.7 GHz was not detected with the APEX telescope toward this position. These D2H+ observations complement our previous detections of para-H2D+ and ortho-H2D+ using SOFIA and APEX. By modeling chemistry and radiative transfer in the dense core surrounding the protostars, we find that the ortho-D2H+ and para-H2D+ absorption features mainly originate in the cool (T<18 K) outer envelope of the core. In contrast, the ortho-H2D+ emission from the core is significantly absorbed by the ambient molecular cloud. Analyses of the combined D2H+ and H2D+ data result in an age estimate of ~500 000 yr for the core, with an uncertainty of ~200 000 yr. The core material has probably been pre-processed for another 500 000 years in conditions corresponding to those in the ambient molecular cloud. The inferred time scale is more than ten times the age of the embedded protobinary. The D2H+ and H2D+ ions have large and nearly equal total (ortho+para) fractional abundances of ~$10^{-9}$ in the outer envelope. This confirms the central role of H3+ in the deuterium chemistry in cool, dense gas, and adds support to the prediction of chemistry models that also D3+ should be abundant in these conditions.

astro-ph.GA↗

arXiv2016

Molecular Polymorphism: Microwave Spectra, Equilibrium Structures, and an Astronomical Investigation of the HNCS Isomeric Family

The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry-Pérot Fourier-transform microwave spectroscopy between 6 and 40~GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35-37~kcal/mol less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation-vibration calculated theoretically. Formation and isomerization pathways have also been investigated; the high abundance of HSCN relative to ground state HNCS, and the detection of strong lines of SH using CH$_3$CN and H$_2$S, suggest that HSCN is preferentially produced by the radical-radical reaction HS + CN. A radio astronomical search for HSCN and its isomers has been undertaken toward the high-mass star-forming region Sgr B2(N) in the Galactic Center with the 100 m Green Bank Telescope. While we find clear evidence for HSCN, only a tentative detection of HNCS is proposed, and there is no indication of HCNS or HSNC at the same rms noise level. HSCN, and tentatively HNCS, displays clear deviations from a single-excitation temperature model, suggesting weak masing may be occurring in some transitions in this source.

astro-ph.GA↗

arXiv2016

Chemical differentiation in a prestellar core traces non-uniform illumination

Dense cloud cores present chemical differentiation due to the different distribution of C-bearing and N-bearing molecules, the latter being less affected by freeze-out onto dust grains. In this letter we show that two C-bearing molecules, CH$_3$OH and $c$-C$_3$H$_2$, present a strikingly different (complementary) morphology while showing the same kinematics toward the prestellar core L1544. After comparing their distribution with large scale H$_2$ column density N(H$_2$) map from the Herschel satellite, we find that these two molecules trace different environmental conditions in the surrounding of L1544: the $c$-C$_3$H$_2$ distribution peaks close to the southern part of the core, where the surrounding molecular cloud has a N(H$_2$) sharp edge, while CH$_3$OH mainly traces the northern part of the core, where N(H$_2$) presents a shallower tail. We conclude that this is evidence of chemical differentiation driven by different amount of illumination from the interstellar radiation field: in the South, photochemistry maintains more C atoms in the gas phase allowing carbon chain (such as $c$-C$_3$H$_2$) production; in the North, C is mainly locked in CO and methanol traces the zone where CO starts to freeze out significantly. During the process of cloud contraction, different gas and ice compositions are thus expected to mix toward the central regions of the core, where a potential Solar-type system will form. An alternative view on carbon-chain chemistry in star-forming regions is also provided.

astro-ph.GA↗

arXiv2016

Laboratory rotational ground state transitions of NH$_3$D$^+$ and CF$^+$

Aims. This paper reports accurate laboratory frequencies of the rotational ground state transitions of two astronomically relevant molecular ions, NH3D+ and CF+. Methods. Spectra in the millimeter-wave band were recorded by the method of rotational state-selective attachment of He-atoms to the molecular ions stored and cooled in a cryogenic ion trap held at 4 K. The lowest rotational transition in the A state (ortho state) of NH$_3$D$^+$ ($J_K = 1_0 - 0_0$), and the two hyperfine components of the ground state transition of CF$^+$($J = 1 - 0$) were measured with a relative precision better than $10^{-7}$. Results. For both target ions the experimental transition frequencies agree with recent observations of the same lines in different astronomical environments. In the case of NH$_3$D$^+$ the high-accuracy laboratory measurements lend support to its tentative identification in the interstellar medium. For CF$^+$ the experimentally determined hyperfine splitting confirms previous quantum-chemical calculations and the intrinsic spectroscopic nature of a double-peaked line profile observed in the $J = 1 - 0$ transition towards the Horsehead PDR.

astro-ph.IM↗