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Oskar Asvany

Publications and source records attributed to Oskar Asvany.

15 recordsLinked to original sources

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

Hyperfine-Resolved Rovibrational and Rotational Spectroscopy of OH$^+$ ($X ^3Σ^-$)

The OH$^+$ ($X ^3Σ^-$) radical cation has been investigated by combining a 4 K 22-pole ion trap apparatus with high-resolution IR and THz radiation sources. Applying different types of action spectroscopic methods, the fundamental vibrational band in the 3 $μ$m range and the spin manifold of the $N=1 \leftarrow 0$ rotational transition around 1 THz have been extended and refined. Additionally, the spin manifold of the $N=2 \leftarrow 1$ rotational transition, scattered around 2 THz, has been measured for the first time with microwave accuracy. Although all hyperfine components of the pure rotational transitions are affected by considerable Zeeman splittings, a simulation of their contours allowed us to extract the field-free center frequencies with high accuracy. A global fit combining rovibrational and pure rotational transitions from the literature with those newly obtained in this work was performed, leading to improvements in the spectroscopic constants of OH$^+$, particularly those in the ground vibrational state.

physics.atm-clus

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

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

Spectroscopic Detection and Characterization of Cyanooxomethylium, NCCO$^+$

Cyanooxomethylium, NCCO$^+$, a fundamental linear acylium ion, has been observed spectroscopically for the first time using action spectroscopy in ion trap apparatuses. A first low-resolution infrared spectrum was obtained between 500 to 1400 cm$^{-1}$ and 2000 to 2500 cm$^{-1}$ using the Free Electron Laser for Infrared eXperiments (FELIX) and the FELion apparatus, employing infrared predissociation of the weakly bound NCCO$^+$-Ne complex. Subsequently, high-resolution studies of the bare ion were performed with the COLtrap II setup, one targeted at the CN-stretching mode $ν_2$ around 2150 cm$^{-1}$ using leak-out spectroscopy and one at the pure rotational spectrum employing a leak-out infrared/millimeter-wave double resonance approach covering transition frequencies as high as 246 GHz. Spectroscopic detection and analysis were guided by high-level quantum-chemical calculations performed at the CCSD(T) level of theory. The collected data permit accurate frequency predictions to support future astronomical searches with sensitive radio telescopes.

physics.chem-ph

Hyperfine-Resolved Rotational Spectroscopy of HCNH+

The rotational spectrum of the molecular ion HCNH+ is revisited using double-resonance spectroscopy in an ion trap apparatus, with six transitions measured between 74 and 445 GHz. Due to the cryogenic temperature of the trap, the hyperfine splittings caused by the 14N quadrupolar nucleus were resolved for transitions up to J = 4-3, allowing for a refinement of the spectroscopic parameters previously reported, especially the quadrupole coupling constant eQq.

physics.chem-ph

High Resolution Rovibrational and Rotational Spectroscopy of H$_2$CCCH$^+$

The rovibrational spectrum of the molecular ion H$_2$CCCH$^+$ was investigated in a 4~K cryogenic ion trap instrument employing the leak-out spectroscopy method. Transitions within the fundamental $ν_1$ (C-H stretch) and the combination band $ν_3$+$ν_5$ (C-C stretches) were detected, the search aided by high level quantum chemical calculations. The analysis of the rovibrational measurements enabled us to predict the rotational structure of the ground state. Using a rotational-vibrational double-resonance scheme, 14 pure rotational transitions were measured. This, in turn, led to the radio astronomical detection of H$_2$CCCH$^+$ in the interstellar medium, as recently reported (Silva et al., Astron. Astrophys. 676, L1, 2023).

physics.chem-ph

Formation of the Methyl Cation by Photochemistry in a Protoplanetary Disk

Forty years ago it was proposed that gas phase organic chemistry in the interstellar medium was initiated by the methyl cation CH3+, but hitherto it has not been observed outside the Solar System. Alternative routes involving processes on grain surfaces have been invoked. Here we report JWST observations of CH3+ in a protoplanetary disk in the Orion star forming region. We find that gas-phase organic chemistry is activated by UV irradiation.

astro-ph.GA

High-resolution spectroscopy of the $ν_3$ antisymmetric C-H stretch of C$_2$H$_2^+$ using leak-out action spectroscopy

The antisymmetric C-H stretching vibration $ν_3$ ($^2Π$ $\leftarrow$ $^2Π$) of ionized acetylene, C$_2$H$_2^+$, has been revisited using a cryogenic 22-pole ion trap machine. Two action spectroscopic techniques, the novel leak-out spectroscopy (LOS) method and the more established laser-induced reactions (LIR) method, are applied and compared. Mass selectivity and cryogenic temperatures down to 4~K enabled the observation of uncontaminated spectra in which the $Λ$-doubling components of this open-shell molecule are mostly well resolved, leading to a slight refinement of the spectroscopic parameters.

physics.chem-ph

Leak-out Spectroscopy, a universal method of action spectroscopy in cold ion traps

A novel method of spectroscopy in ion traps termed leak-out spectroscopy (LOS) is presented. Here, mass selected, cold ions are excited by an infrared laser. In a subsequent collision with a neutral buffer gas particle their internal energy is then transferred to kinetic energy. As a result, these ions leak out from the ion trap and are detected. The LOS scheme is generally applicable, very sensitive and close to background free when operated at low temperature. The potential of this method is demonstrated and characterized here for the first time by recording the rotationally resolved spectrum of the C-H stretching vibration $ν_1$ of linear C$_3$H$^+$. Besides performing high-resolution spectroscopy, this method opens up the way for analyzing the composition of trap content, e.g., determining isomer ratios, by selectively expelling isomers or other isobaric ions from the trap. Likewise, LOS can be used to prepare clean samples of structural and nuclear spin isomers.

physics.chem-ph

High-resolution infrared action spectroscopy of the fundamental vibrational band of CN+

Rotational-vibrational transitions of the fundamental vibrational modes of the $^{12}$C$^{14}$N$^+$ and $^{12}$C$^{15}$N$^+$ cations have been observed for the first time using a cryogenic ion trap apparatus with an action spectroscopy scheme. The lines P(3) to R(3) of $^{12}$C$^{14}$N$^+$ and R(1) to R(3) of $^{12}$C$^{15}$N$^+$ have been measured, limited by the trap temperature of approximately 4 K and the restricted tuning range of the infrared laser. Spectroscopic parameters are presented for both isotopologues, with band origins at 2000.7587(1) and 1970.321(1) cm$^{-1}$, respectively, as well as an isotope independent fit combining the new and the literature data.

physics.chem-ph

Rovibrational spectroscopy of the CH$^+$-He and CH$^+$-He$_4$ complexes

A cryogenic 22-pole ion trap apparatus is used in combination with a table-top pulsed IR source to probe weakly bound CH$^+$-He and CH$^+$-He$_4$ complexes by predissociation spectroscopy at 4 K. The infrared photodissociation spectra of the C-H stretching vibrations are recorded in the range of 2720-2800 cm$^{-1}$. The spectrum of CH$^+$-He exhibits perpendicular transitions of a near prolate top with a band origin at 2745.9 cm$^{-1}$, and thus confirms it to have a T-shaped structure. For CH$^+$-He$_4$, the C-H stretch along the symmetry axis of this oblate top results in parallel transitions.

physics.chem-ph

First laboratory detection of vibration-rotation transitions of CH$^+$ and $^{13}$CH$^+$ and improved measurement of their rotational transition frequencies

The long-searched C-H stretches of the fundamental ions CH$^+$ and $^{13}$CH$^+$ have been observed for the first time in the laboratory. For this, the state-dependent attachment of He atoms to these ions at cryogenic temperatures has been exploited to obtain high-resolution rovibrational data. In addition, the lowest rotational transitions of CH$^+$, $^{13}$CH$^+$ and CD$^+$ have been revisited and their rest frequency values improved substantially.

astro-ph.GA

Accurate frequency determination of vibration-rotation and rotational transitions of SiH+

The fundamental 28SiH+ ion has been characterized in a collaborative work, utilizing a hollow-cathode-discharge laser-spectrometer and a cryogenic ion trap spectrometer. Twenty-three vibration-rotation transitions around 4.75 um have been detected with high accuracy. This has facilitated the first direct measurement of the pure rotational transition J=1<-0 at 453056.3632(4) MHz in the trap spectrometer. The measured and accurately predicted transitions enable the search for this ion in space with IR and sub-mm telescopes.

astro-ph.GA

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