arXiv subjects

Pavol Jusko

Publications and source records attributed to Pavol Jusko.

17 recordsLinked to original sources

arXiv2026

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

The OH$^+$ ($X ^3\Sigma^-$) 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 $\mu$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↗

arXiv2026

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

In this work, we report on the high-resolution infrared spectrum of CCH$^+$ ($^3\Pi$) 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 $\Lambda$-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 $\Omega = 2$ 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

Broadband infrared spectroscopy of methanol isotopologues in pure, H2O-rich, and CO-rich ice analogues

Deuterium fractionation is highly efficient during the early stages of star formation, particularly in starless and prestellar cores where temperatures are low (<10 K) and molecular freeze-out onto dust grains is significant. Methanol forms early in these environments following CO freeze-out via successive hydrogenation reactions on grain surfaces, while the production of deuterated methanol requires elevated gas-phase D/H ratios generated through dissociative recombination of deuterated H3+. Consequently, large abundances of deuterated methanol are observed toward young stellar objects where prestellar ices have recently sublimated. Here, we present laboratory infrared spectra of methanol and its deuterated isotopologues in astrophysical ice analogues, complemented by anharmonic vibrational calculations used to guide band assignments. Experiments were performed at the CASICE laboratory using a Bruker Vertex 70v spectrometer coupled to a closed-cycle helium cryostat, with isotopologue ices deposited at 10 K under high-vacuum conditions. Infrared transmission spectra were recorded over 6000-30 cm-1 (1.67-333 um) and compared with spectra of pure isotopologue ices. Distinctive mid-infrared band patterns are identified for each deuterated species. In particular, CH2DOH exhibits a characteristic doublet at 1293 and 1326 cm-1 (7.73 and 7.54 um), while CHD2OH shows a similar doublet at 1301 and 1329 cm-1 (7.69 and 7.52 um), both remaining largely invariant across all studied ice mixtures. These robust spectral signatures provide reliable tracers for identifying deuterated methanol in JWST observations and for constraining astrochemical gas-grain models of deuterium enrichment prior to star and planet formation.

astro-ph.GA↗

arXiv2025

High Resolution Overtone Spectroscopy of HNC$^+$ and HCN$^+$

Rotationally resolved spectra of the HNC$^+$ and HCN$^+$ molecular ions have been recorded in the spectral range between 6200 and 6800 \rcm\ using a cryogenic ion trap instrument. The rovibrational transitions were probed using two different action spectroscopy schemes, namely laser-induced reaction (LIR) and leak-out spectroscopy (LOS). Various vibrational bands of HNC$^+$ and HCN$^+$ were measured with high resolution for the first time. For HNC$^+$, the $\text{X}~^2\Sigma^+~(20^00)-(00^00)$ overtone band was recorded using LIR, while LOS was used to probe the $\text{X}~^2\Pi~(000)^1-(210)^0\mu$ combination band and the $\text{X}~^2\Pi~(000)^1-\text{A}~^2\Sigma^+~(10^00)$ vibronic band of HCN$^+$. Spectroscopic constants, band origins and radiative lifetimes for the observed states have been determined. The effective fit for the HCN$^+$ spectra revealed the presence of strong vibrational couplings leading to perturbations of the rovibrational levels of the excited states. The two action spectroscopy schemes are compared and their potential use to explore ion-molecule interactions is discussed.

astro-ph.SR↗

arXiv2025

Near-infrared high resolution overtone spectroscopy of the hydronium ion H$_3$O$^+$: the $2\nu_3^{2+}$ and $2\nu_3^{2-}$ bands

This work presents the rovibrational spectra of the two strongest first overtone bands of the asymmetric stretching mode $\nu_3$ ($2\nu_3^{2+}$ and $2\nu_3^{2-}$) of the hydronium ion, H$_3$O$^+$. The measurements were performed in a temperature-variable cryogenic 22 pole ion trap using leak-out spectroscopy (LOS), covering an energy range of $6750-6950$ cm$^{-1}$. The spectra were fit with a standard oblate symmetric top Hamiltonian and additional off-diagonal matrix elements accounting for $l$-doubling to obtain the spectroscopic constants and the band origins, which were determined to be $6845.610(14)$ cm$^{-1}$ for $2\nu_3^{2+}$ and $6878.393(13)$ cm$^{-1}$ for $2\nu_3^{2-}$.

physics.atom-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 {\mu}m 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↗

arXiv2025

Rovibrational Overtone and Combination Bands of the HCNH+ Ion

Spectra of vibrational overtone and combination bands from vibrational ground state of HCNH+ were measured using an action spectroscopy technique with active background suppression in a cryogenic 22 pole radio frequency ion trap apparatus. Spectroscopic constants for the upper vibrational levels of the transitions were determined with vibrational band origins being 6846.77981(90) $\text{cm}^{-1}$ ($2\nu_1$ , NH stretch), 6640.47624(43) $\text{cm}^{-1}$ ($\nu_1 + \nu_2$), 6282.03578(63) $\text{cm}^{-1}$ ($2\nu_2$, CH stretch), and 6588.4894(20) $\text{cm}^{-1}$ ($\nu_2 + \nu_3 + 2\nu_5^0$). State of the art ab initio VCI calculations up to 10000 $\text{cm}^{-1}$ complement the experimental data.

astro-ph.GA↗

arXiv2025

Cl+ and HCl+ in Reaction with H2 and Isotopologues: A Glance into H Abstraction and Indirect Exchange at Astrophysical Conditions

Astrochemical models of interstellar clouds, the sites of stars, and planet formation require information about spin-state chemistry to allow quantitative comparison with spectroscopic observations. In particular, it is important to know if full scrambling or H abstraction (also known as proton hopping) takes place in ion-neutral reactions. The reaction of Cl+ and HCl+ with H2 and isotopologues has been studied at cryogenic temperatures between 20 and 180 K using a 22 pole radio frequency ion trap. Isotopic exchange processes are used to probe the reaction mechanism of the HCl+ + H2 reaction. The results are compared with previous measurements and theoretical predictions. The rate coefficients for the Cl+ + H2 and HCl+ + H2 reactions are found to be constant in the range of temperatures studied, except for the DCl+ + D2 reaction, where a weak negative temperature dependence is observed, and reactions with D2 are found to be significantly slower than the Langevin rate. No isotopic exchange reactions are observed to occur for the H2Cl+ ion. The analysis of the products of the HCl+ + H2 isotopic system clearly indicates that the reaction proceeds via simple hydrogen atom abstraction.

astro-ph.EP↗

arXiv2025

Ion-kinetic-energy sampling in a 22-pole trap using ring-electrode evaporation

We present an experimental method for the characterization of the kinetic energies of ions confined in a 22-pole radio frequency trap by inducing a small potential barrier using the surrounding ring electrodes, allowing the selective extraction of ions. Energy sampling experiments have been performed on buffer gas thermalized He$^+$ ions at trap temperatures between 10-180 K, resulting in distinct extraction curves as a function of the potential barrier, and a differentiated behavior depending on the escape time from the trap. The experiments are complemented by Monte Carlo simulations of the ion trajectories inside the calculated trap potential and allow us to investigate the properties of the sampling method, the role of ion motion coupling, and the impact of residual buffer gas collisions on the observed results. The technique has also been successfully applied to identify energetic H$_3^+$ ions produced in an exothermic reaction inside the trap. Upon calibration, this method can provide relative kinetic energy distributions or be used to filter the maximum desired kinetic energy of the ions inside the trap.

physics.atom-ph↗

arXiv2024

Measurements and simulations of rate coefficients for the deuterated forms of the H2 + + H2 and H3 + + H2 reactive systems at low temperature

The rate coefficients of various isotopic variations of the H2+ + H2 and H3+ + H2 reactions in the 10-250 K temperature range were measured using a cryogenic 22 pole radio frequency ion trap. The processes involving diatomic ions were found to behave close to the Langevin rate, whereas temperature-dependent rate coefficients were obtained for the four isotopic exchange processes with triatomic ions. Fitting the experimental data using a chemical code allowed us in specific cases to constrain rate coefficients that were not directly measured in the ion trap. The reported rate coefficients suggest a more efficient hydrogenation of deuterated H3+ forms than usually assumed in astrochemical models, which might affect deuteration rates in warmer environments.

astro-ph.SR↗

arXiv2024

Overtone Transition $2ν_1$ of $\text{HCO}^+$ and $\text{HOC}^+$: Origin, Radiative Lifetime, Collisional Quenching

We present spectra of the first overtone vibration transition of $\text{C-H}$/$\text{O-H}$ stretch ($2ν_1$) in $\text{HCO}^+$ and $\text{HOC}^+$, recorded using a laser induced reaction action scheme inside a cryogenic 22 pole radio frequency trap. Band origins have been located at 6078.68411(19) and 6360.17630(26) $\text{cm}^{-1}$, respectively. We introduce a technique based on mass selective ejection from the ion trap for recording background free action spectra. Varying the number density of the neutral action scheme reactant ($\text{CO}_2$ and Ar, respectively) and collisional partner reactant inside the ion trap, permitted us to estimate the radiative lifetime of the state to be 1.53(34) and 1.22(34) ms, respectively, and the collisional quenching rates of $\text{HCO}^+$ ($2ν_1$) with He, H$_2$, and N$_2$.

physics.atom-ph↗

arXiv2023

Measurements of rate coefficients of CN$^+$, HCN$^+$ and HNC$^+$ collisions with H$_2$ at cryogenic temperatures

The experimental determination of the reaction rate coefficients for production and destruction of $\text{HCN}^+$ and $\text{HNC}^+$ in collisions with $\text{H}_2$ is presented. A variable temperature 22 pole radio frequency ion trap was used to study the reactions in the temperature range of $17 - 250\;\text{K}$. The obtained rate coefficients for the reaction of $\text{CN}^+$ and of $\text{HCN}^+$ with $\text{H}_2$ are close to the collisional (Langevin) value, whereas that for the reaction of $\text{HNC}^+$ with $\text{H}_2$ is quickly decreasing with increasing temperature. The product branching ratios for the reaction of $\text{CN}^+$ with $\text{H}_2$ are also reported and show a notable decrease of $\text{HNC}^+$ product with respect to $\text{HCN}^+$ product with increasing temperature. These measurements have consequences for current astrochemical models of cyanide chemistry, in particular for the $\text{HCNH}^+$ cation.

astro-ph.GA↗

arXiv2023

Cold CAS Ion Trap -- 22 pole trap with ring electrodes for astrochemistry

The enhancement of a cryogenic radio frequency 22 pole trap instrument by the addition of ring electrodes is presented in detail. The ring electrodes tightly surround the poles and only a fraction of the applied electric potential penetrates to the trap axis, facilitating the fine control of slow cold ions. A precise computational model, describing the effective mechanical potential created by the applied static and rf fields, governing the ion behaviour, is employed to demonstrate and understand the operation of our setup. The use of ring electrodes for improved extraction of cold stored ions is shown. Variable trapping potentials, placed on one ring electrode, can be used to control the evaporation of only those $\text{H}^+$ ions from the trap, whose kinetic energy exceeds the barrier. This ring electrode trapping opens new possibilities to study processes of minimal kinetic energy release, e. g. spin exchange. We propose a robust modified method for the determination of temperature dependent ion molecule reaction rates, resistant to effects caused by neutral gas freezing and demonstrate it on the reaction of $\text{CO}^+$/$\text{CO}_2^+$ with $\text{H}_2$/$\text{D}_2$. Finally, the use of a supercontinuum laser for quick localisation of spectroscopic bands is examined on the $\text{N}_2^+$ Meinel system.

physics.chem-ph↗

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↗

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↗

arXiv2018

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↗