Paola Caselli

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 $\text{X}~^2Σ^+~(20^00)-(00^00)$ overtone band was recorded using LIR, while LOS was used to probe the $\text{X}~^2Π~(000)^1-(210)^0μ$ combination band and the $\text{X}~^2Π~(000)^1-\text{A}~^2Σ^+~(10^00)$ 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.

This work presents the rovibrational spectra of the two strongest first overtone bands of the asymmetric stretching mode $ν_3$ ($2ν_3^{2+}$ and $2ν_3^{2-}$) 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 $2ν_3^{2+}$ and $6878.393(13)$ cm$^{-1}$ for $2ν_3^{2-}$.

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.

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) $\text{cm}^{-1}$ ($2ν_1$ , NH stretch), 6640.47624(43) $\text{cm}^{-1}$ ($ν_1 + ν_2$), 6282.03578(63) $\text{cm}^{-1}$ ($2ν_2$, CH stretch), and 6588.4894(20) $\text{cm}^{-1}$ ($ν_2 + ν_3 + 2ν_5^0$). State of the art ab initio VCI calculations up to 10000 $\text{cm}^{-1}$ complement the experimental data.

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.

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.

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.

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$_2$.

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.

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.