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Kim Steenbakkers

Publications and source records attributed to Kim Steenbakkers.

3 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↗

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↗