Ionic fragmentation products of benzonitrile as important intermediates in the growth of polycyclic aromatic hydrocarbons.

In various astronomical environments such as the interstellar medium or (exo)planetary atmospheres, an interplay of bottom-up growth and top-down destruction processes of (polycyclic) aromatic hydrocarbons (PAHs) takes place. To get more insight into the interplay of both processes, we disentangle the fragmentation and formation processes that take place upon dissociative ionization of benzonitrile. We build on previous spectroscopic detections of the ionic fragmentation products of benzonitrile and use these as reactants for low-temperature bottom-up ion-molecule reactions with acetylene. By combining kinetics and infrared action spectroscopy, we reveal exothermic pathways to various (polycyclic) aromatic molecules, including the pentalene and phenylacetylene radical cations. We determine the reaction rate coefficients and unambiguously assign the structures of the reaction products. The data is supplemented by potential energy surface calculations and the analysis of non-covalent interactions. This study shows the unexpected formation of a linked four- and six-membered ring structure (phenylcyclobutadiene radical cation) with molecular formula C10H8˙+, and not the commonly observed isomer naphthalene˙+. All observed reactions proceed via radiative association processes and are relevant for the chemistry in (cold) astrochemical environments.

Gas-Phase Infrared Action Spectroscopy of CH2Cl+ and CH3ClH+: Likely Protagonists in Chlorine Astrochemistry.

Two fundamental halocarbon ions, CH2Cl+ and CH3ClH+, were studied in the gas phase using the FELion 22-pole ion trap apparatus and the Free Electron Laser for Infrared eXperiments (FELIX) at Radboud University, Nijmegen (the Netherlands). The vibrational bands of a total of four isotopologs, CH235,37Cl+ and CH335,37ClH+, were observed in selected wavenumber regions between 500 and 2900 cm-1 and then spectroscopically assigned based on the results of anharmonic force field calculations performed at the CCSD(T) level of theory. As the infrared photodissociation spectroscopy scheme employed probes singly Ne-tagged weakly bound complexes, complementary quantum-chemical calculations of selected species were also performed. The impact of tagging on the vibrational spectra of CH2Cl+ and CH3ClH+ is found to be virtually negligible for most bands; for CH3ClH+-Ne, the observations suggest a proton-bound structural arrangement. The experimental band positions as well as the best estimate rotational molecular parameters given in this work provide a solid basis for future spectroscopic studies at high spectral resolutions.

Leak-out spectroscopy as alternative method to rare-gas tagging for the Renner-Teller perturbed HCCH+ and DCCD+ ions.

Infrared messenger-tagging predissociation action spectroscopy (IRPD) is a well-established technique to record vibrational spectra of reactive molecular ions. One of its major drawbacks is that the spectrum of the messenger-ion complex is taken instead of that of the bare ion. In particular for small open-shell species, such as the Renner-Teller (RT) affected HCCH+ and DCCD+, the attachment of the tag may have a significant impact on the spectral features. Here we present the application of the novel leak-out spectroscopy (LOS) as a tag-free method to record the cis-bending of the HCCH+ (∼700 cm-1) and DCCD+ cations (∼520 cm-1), using a cryogenic ion trap end user station at the FELIX laboratory. We demonstrate that the obtained LOS spectrum is equivalent to a previously recorded laser-induced reactions (LIR) spectrum of HCCH+. The bending modes are the energetically lowest-lying vibrational modes targeted with LOS so far, showing its potential as a universal broadband spectroscopic technique. Furthermore, we have investigated the effect of the rare gas attachment by recording the vibrational spectra of Ne- and Ar-tagged HCCH+. We found that the Ne-attachment led to a shift in band positions and change in relative intensities, while the Ar-attachment even led to a complete quenching of the RT splitting, showing the importance of using a tag-free method for RT affected systems. The results are interpreted with the help of high-level ab initio calculations in combination with an effective Hamiltonian approach.

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory.

The cationic fragmentation products in the dissociative ionization of pyridine and benzonitrile have been studied by infrared action spectroscopy in a cryogenic ion trap instrument at the Free-Electron Lasers for Infrared eXperiments (FELIX) Laboratory. A comparison of the experimental vibrational fingerprints of the dominant cationic fragments with those from quantum chemical calculations revealed a diversity of molecular fragment structures. The loss of HCN/HNC is shown to be the major fragmentation channel for both pyridine and benzonitrile. Using the determined structures of the cationic fragments, potential energy surfaces have been calculated to elucidate the nature of the neutral fragment partner. In the fragmentation chemistry of pyridine, multiple non-cyclic structures are formed, whereas the fragmentation of benzonitrile dominantly leads to the formation of cyclic structures. Among the fragments are linear cyano-(di)acetylene˙+, methylene-cyclopropene˙+ and o- and m-benzyne˙+ structures, the latter possible building blocks in interstellar polycyclic aromatic hydrocarbon (PAH) formation chemistry. Molecular dynamics simulations using density functional based tight binding (MD/DFTB) were performed and used to benchmark and elucidate the different fragmentation pathways based on the experimentally determined structures. The implications of the difference in fragments observed for pyridine and benzonitrile are discussed in an astrochemical context.

Vibrational Predissociation Spectra of C2 N- and C3 N- : Bending and Stretching Vibrations.

We present infrared predissociation spectra of C2 N- (H2 ) and C 3 N- (H2 ) in the 300-1850 cm-1 range. Measurements were performed using the FELion cryogenic ion trap end user station at the Free Electron Lasers for Infrared eXperiments (FELIX) laboratory. For C2 N- (H2 ), we detected the CCN bending and CC-N stretching vibrations. For the C3 N- (H2 ) system, we detected the CCN bending, the CC-CN stretching, and multiple overtones and/or combination bands. The assignment and interpretation of the presented experimental spectra is validated by calculations of anharmonic spectra within the vibrational configuration interaction (VCI) approach, based on potential energy surfaces calculated at explicitly correlated coupled cluster theory (CCSD(T)-F12/cc-pVTZ-F12). The H2 tag acts as an innocent spectator, not significantly affecting the C2,3 N- bending and stretching mode positions. The recorded infrared predissociation spectra can thus be used as a proxy for the vibrational spectra of the bare anions.

A vibrational action spectroscopic study of the Renner-Teller- and spin-orbit-affected cyanoacetylene radical cation HC3N.

The linear radical cation of cyanoacetylene, HC3N+ (2Π), is not only of astrophysical interest, being the, so far undetected, cationic counterpart of the abundant cyanoaceteylene, but also of fundamental spectroscopic interest due to its strong spin-orbit and Renner-Teller interactions. Here, we present the first broadband vibrational action spectroscopic investigation of this ion through the infrared pre-dissociation (IRPD) method using a Ne tag. Experiments have been performed using the FELion cryogenic ion-trap instrument in combination with the FELIX free-electron lasers and a Laservision optical parametric oscillator/optical parametric amplifier system. The vibronic splitting patterns of the three interacting bending modes (ν5, ν6, ν7), ranging from 180 to 1600 cm-1, could be fully resolved revealing several bands that were previously unobserved. The associated Renner-Teller and intermode coupling constants have been determined by fitting an effective Hamiltonian to the experimental data, and the obtained spectroscopic constants are in reasonable agreement with previous photoelectron spectroscopy (PES) studies and ab initio calculations on the HC3N+ ion. The influence of the attached Ne atom on the infrared spectrum has been investigated by ab initio calculations at the RCCSD(T)-F12a level of theory, which strongly indicates that the discrepancies between the IRPD and PES data are a result of the effects of the Ne attachment.

Formation of the acenaphthylene cation as a common C2H2-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene.

Polycyclic aromatic hydrocarbons (PAHs) are thought to be a major constituent of astrophysical environments, being the carriers of the ubiquitous aromatic infrared bands (AIBs) observed in the spectra of galactic and extra-galactic sources that are irradiated by ultraviolet (UV) photons. Small (2-cycles) PAHs were unambiguously detected in the TMC-1 dark cloud, showing that PAH growth pathways exist even at low temperatures. The processing of PAHs by UV photons also leads to their fragmentation, which has been recognized in recent years as an alternative route to the generally accepted bottom-up chemical pathways for the formation of complex hydrocarbons in UV-rich interstellar regions. Here we consider the C12H8+ ion that is formed in our experiments from the dissociative ionization of the anthracene and phenanthrene (C14H10) molecules. By employing the sensitive action spectroscopic scheme of infrared pre-dissociation (IRPD) in a cryogenic ion trap instrument coupled to the free-electron lasers at the FELIX Laboratory, we have recorded the broadband and narrow line-width gas-phase IR spectra of the fragment ions (C12H8+) and also the reference spectra of three low energy isomers of C12H8+. By comparing the experimental spectra to those obtained from quantum chemical calculations we have identified the dominant structure of the fragment ion formed in the dissociation process to be the acenaphthylene cation for both isomeric precursors. Ab initio molecular dynamics simulations are presented to elucidate the fragmentation process. This result reinforces the dominant role of species containing a pentagonal ring in the photochemistry of small PAHs.

Polycyclic aromatic hydrocarbon growth in a benzene discharge explored by IR-UV action spectroscopy.

Infrared signatures of polycyclic aromatic hydrocarbons (PAHs) are detected towards many phases of stellar evolution. PAHs are major players in the carbon chemistry of the interstellar medium, forming the connection between small hydrocarbons and large fullerenes. However, as details on the formation of PAHs in these environments are still unclear, modeling their abundance and chemistry has remained far from trivial. By combining molecular beam mass-selective IR spectroscopy and calculated IR spectra, we analyze the discharge of benzene and identify resulting products including larger PAHs, radicals and intermediates that serve as promising candidates for radio astronomical searches. The identification of various reaction products indicates that different gas-phase reaction mechanisms leading to PAH growth must occur under the same conditions to account for all observed PAH-related species, thereby revealing the complex and interconnected network of PAH formation pathways. The results of this study highlight key (exothermic) reactions that need to be included in astrochemical models describing the carbon chemistry in our universe.

Spectroscopic Detection of Cyano-Cyclopentadiene Ions as Dissociation Products upon Ionization of Aniline.

The H-loss products (C6H6N+) from the dissociative ionization of aniline (C6H7N) have been studied by infrared predissociation spectroscopy in a cryogenic ion trap instrument at the free electron laser for infrared experiments (FELIX) laboratory. Broadband and narrow line width vibrational spectra in the spectral fingerprint region of 550-1800 cm-1 have been recorded. The comparison to calculated spectra of the potential isomeric structures of the fragment ions reveals that the dominant fragments are five-membered cyano-cyclopentadiene ions. Computed C6H7N•+ potential energy surfaces suggest that the dissociation path leading to H loss starts with an isomerization process, following a similar trajectory as the one leading to HNC loss. The possible presence of cyano-cyclopentadiene ions and related five-membered ring species in Titan's atmosphere and the interstellar medium are discussed.

Unidirectional Double- and Triple-Hydrogen Rearrangement Reactions Probed by Infrared Ion Spectroscopy.

Unidirectional double-hydrogen (2H) and triple-hydrogen (3H) rearrangement reactions occur upon electron-ionization-induced fragmentation of trans-2-(4-N,N-dimethylaminobenzyl)-1-indanol (1), trans-2-(4-methoxybenzyl)-1-indanol (2), 4-(4-N,N-dimethylaminophenyl)-2-butanol (3), and related compounds, as reported some 35 years ago (Kuck, D.; Filges, U. Org. Mass Spectrom. 1988, 23, 643-653). These unusual intramolecular redox processes were found to dominate the mass spectra of long-lived, metastable ions. The present report provides independent evidence for the structures of the product ions formed by the 2H and 3H rearrangement in an ion trap instrument. The radical cations 1•+ and 3•+ as well as ionized 1-(4-N,N-dimethylaminophenyl)-5-(4-methoxyphenyl)-3-pentanol, 5•+, were generated by electrospray ionization from anhydrous acetonitrile solutions. The 2H and 3H fragment ions were obtained by collision-induced dissociation and characterized by IR ion spectroscopy and density functional theory calculations. Comparison of the experimental and calculated infrared ion spectra enabled the identification of the 2H rearrangement product ion, C9H14N+ (m/z 136), as an N,N-dimethyl-para-toluidinium ion bearing the extra proton ortho to the amino group, a tautomer which was calculated to be 31 kJ/mol less stable than the corresponding N-protonated form. The 3H rearrangement product ion, C8H13N•+ (m/z 123), formerly assumed to be a distonic ammonium ion bearing a cyclohexadienyl radical, was now identified as a conventional radical cation, ionized N,N-dimethyl-2,3-dihydro-para-toluidine. Thus, the 3H rearrangement represents an intramolecular transfer hydrogenation between a secondary alcohol and an ionized aromatic ring. Based on these structural assignments, more detailed mechanisms for the unidirectional 2H and 3H rearrangement reactions are proposed.

Strong ortho/para effects in the vibrational spectrum of Cl-(H2).

The predissociation spectrum of the Cl-35(H2) complex is measured between 450 and 800 cm-1 in a multipole radiofrequency ion trap at different temperatures using the FELIX infrared free electron laser. Above a certain temperature, the removal of the Cl-(p-H2) para nuclear spin isomer by ligand exchange to the Cl-(o-H2) ortho isomer is suppressed effectively, thereby making it possible to detect the spectrum of this more weakly bound complex. At trap temperatures of 30.5 and 41.5 K, we detect two vibrational bands of Cl-(p-H2) at 510(1) and 606(1) cm-1. Using accurate quantum calculations, these bands are assigned to transitions to the inter-monomer vibrational modes (v1,v2 l2 ) = (0, 20) and (1, 20), respectively.

Structural investigation of doubly-dehydrogenated pyrene cations.

The vibrationally resolved spectra of the pyrene cation and doubly-dehydrogenated pyrene cation (C16H10˙+; Py+ and C16H8˙+; 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.

Vibrational Excitation Hindering an Ion-Molecule Reaction: The c-C_{3}H_{2}

Experiments within a cryogenic 22-pole ion trap have revealed an interesting reaction dynamic phenomenon, where rovibrational excitation of an ionic molecule slows down a reaction with a neutral partner. This is demonstrated for the low-temperature hydrogen abstraction reaction c-C_{3}H_{2}^{+}+H_{2}, where excitation of the ion into the ν_{7} antisymmetric C-H stretching mode decreased the reaction rate coefficient toward the products c-C_{3}H_{3}^{+}+H. Supported by high-level quantum-chemical calculations, this observation is explained by the reaction proceeding through a c-C_{3}H_{2}^{+}-H_{2} collision complex in the entrance channel, in which the hydrogen molecule is loosely bound to the hydrogen atom of the c-C_{3}H_{2}^{+} ion. This discovery enables high-resolution vibrational action spectroscopy for c-C_{3}H_{2}^{+} and other molecular ions with similar reaction pathways. Moreover, a detailed kinetic model relating the extent of the observed product depletion signal to the rate coefficients of inelastic collisions reveals that rotational relaxation of the vibrationally excited ions is significantly faster than the rovibrational relaxation, allowing for a large fraction of the ions to be vibrationally excited. This result provides fundamental insight into the mechanism for an important class of chemical reactions, and is capable of probing the inelastic collisional dynamics of molecular ions.

Gas-Phase Vibrational Spectroscopy of the Hydrocarbon Cations l-C3H+, HC3H+, and c-C3H2+: Structures, Isomers, and the Influence of Ne-Tagging.

We report the first gas-phase vibrational spectra of the hydrocarbon ions C3H+ and C3H2+. The ions were produced by electron impact ionization of allene. Vibrational spectra of the mass-selected ions tagged with Ne were recorded using infrared predissociation spectroscopy in a cryogenic ion trap instrument using the intense and widely tunable radiation of a free electron laser. Comparison of high-level quantum chemical calculations and resonant depletion measurements revealed that the C3H+ ion is exclusively formed in its most stable linear isomeric form, whereas two isomers were observed for C3H2+. Bands of the energetically favored cyclic c-C3H2+ are in excellent agreement with calculated anharmonic frequencies, whereas for the linear open-shell HCCCH+ (2Πg) a detailed theoretical description of the spectrum remains challenging because of Renner-Teller and spin-orbit interactions. Good agreement between theory and experiment, however, is observed for the frequencies of the stretching modes for which an anharmonic treatment was possible. In the case of linear l-C3H+, small but non-negligible effects of the attached Ne on the ion fundamental band positions and the overall spectrum were found.

The FELion cryogenic ion trap beam line at the FELIX free-electron laser laboratory: infrared signatures of primary alcohol cations.

The combination of a 4 K 22-pole ion trap instrument, FELion, with the widely tunable free electron lasers at the FELIX Laboratory is described in detail. It allows for wide-range infrared vibrational spectroscopy of molecular ions. In this study, the apparatus is used for infrared vibrational predissociation (IR-PD) measurements of the simple alcohol cations of methanol and ethanol as well as their protonated forms. Spectra are taken by tagging the cold molecular ions with He atoms. The infrared spectrum of protonated methanol is recorded for the first time, and the wavelength coverage for all other species is substantially extended. The bands of all spectra are analysed by comparison to ab initio calculation results at different levels of theory. Vibrational bands of different isomers and conformers (rotamers) are discussed and identified in the experimental spectra. Besides the measurement of IR-PD spectra, the method of infrared multiple photon dissociation IR-MPD is applied for some cases. Spectral narrowing due to the cold environment is observed and rotational band contours are simulated. This will help in identifying more complex species using the IR-MPD method in future measurements. Overall the IR-PD spectra reveal more bands than are observed for the IR-MPD spectra. In particular, many new bands are observed in the fingerprint region. Depletion saturation of the finite number of trapped ions is observed for the IR-PD spectra of the ethanol cation and the presence of only one isomeric species is concluded. This special feature of ion trapping spectroscopy may be used in future studies for addressing specific isomers or cleaning the ion cloud from specific isomers or conformers. In addition, the results of this study can be used as a basis to obtain high-resolution infrared vibrational and THz rotational spectra of alcohol ions in order to detect them in space.

Low frequency vibrational anharmonicity and nuclear spin effects of Cl-(H2) and Cl-(D2).

Low frequency combination bands of 35Cl-(H2) and 35Cl-(D2) have been measured in the region between 600 and 1100 cm-1 by infrared predissociation spectroscopy in a cryogenic 22-pole ion trap using a free electron laser at the FELIX Laboratory as a tunable light source. The 35Cl-(H2) (35Cl-(D2)) spectrum contains three bands at 773 cm-1 (620 cm-1), 889 cm-1 (692 cm-1), and 978 cm-1 (750 cm-1) with decreasing intensity toward higher photon energies. Comparison of the experimentally determined transition frequencies with anharmonic vibrational self-consistent field and vibrational configuration interaction calculations suggests the assignment of the combination bands v1 + v2, 2v1 + v2, and 3v1 + v2 for 35Cl-(H2) and 2v1 + v2, 3v1 + v2, and 4v1 + v2 for 35Cl-(D2), where v1 is the 35Cl-⋯H2 stretching fundamental and v2 is the Cl-(H2) bend. The observed asymmetric temperature dependent line shape of the v1 + v2 transition can be modeled by a series of ∑+-∏ ro-vibrational transitions, when substantially decreasing the rotational constant in the vibrationally excited state by 35%. The spectrum of 35Cl-(D2) shows a splitting of 7 cm-1 for the strongest band which can be attributed to the tunneling of the ortho/para states of D2.

Direct Evidence of the Benzylium and Tropylium Cations as the Two Long-Lived Isomers of C7 H7.

Disentangling the isomeric structure of C7 H7 + is a longstanding experimental issue. We report here the full mid-infrared vibrational spectrum of C7 H7 + 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.