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Molecular cluster ions, which are stored in an electromagnetic trap under ultra-high vacuum conditions, undergo blackbody infrared radiative dissociation (BIRD). This process can be simulated with master equation modeling (MEM), predicting temperature-dependent dissociation rate constants, which are very sensitive to the dissociation energy. We have recently introduced a multiple-well approach for master equation modeling, where several low-lying isomers are taken into account. Here, we experimentally measure the BIRD of CO4●–(H2O)1,2 and model the results with a slightly modified multiple-well MEM. In the experiment, we exclusively observe loss of water from CO4●–(H2O), while the BIRD of CO4●–(H2O)2 leads predominantly to loss of carbon dioxide, with water loss occurring to a lesser extent. The MEM of two competing reactions requires empirical scaling factors for infrared intensities and the sum of states of the loose transition states employed in the calculation of unimolecular rate constants so that the simulated branching ratio matches the experiment. The experimentally derived binding energies are ΔH0(CO4●––H2O) = 45 ± 3 kJ/mol, ΔH0(CO4●–(H2O)–H2O) = 41 ± 3 kJ/mol, and ΔH0(CO2–O2●–(H2O)2) = 37 ± 3 kJ/mol. Quantum chemical calculations on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVDZ level, corrected for the basis set superposition error, yield binding energies that are 2–5 kJ/mol higher than experiment, within error limits of both experiment and theory. The relative activation energies for the two competing loss channels are as well fully consistent with theory. [ABSTRACT FROM AUTHOR]

Electronic absorption spectra of water cluster anions (H2O)n-, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid-vacuum interface.

Electronic absorption spectra of water cluster anions (H2O)n-, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid-vacuum interface.

Iron is the most abundant transition metal in the interstellar medium (ISM), and is thought to be involved in a variety of astrochemical processes. Here, we present the infrared multiple photon dissociation (IRMPD) spectra of Ar1,2FeH+ and their deuterated isotopologues in the region of 2240–14 000 cm−1. The Fe–H overtone stretching mode in ArFeH+ and Ar2FeH+ is observed at 3636 ± 28 cm−1 and 3659 ± 13 cm−1, respectively. Deuteration shifts these bands to 2618 ± 31 cm−1 and 2650 ± 14 cm−1 in ArFeD+ and Ar2FeD+, respectively. Additionally, the spectra of Ar2FeH+ and Ar2FeD+ feature broad transitions at ∼2200–4000 cm−1 and ∼4500–6500 cm−1. We assign these bands to electronic transitions from the thermally populated X5A2/X′5A1 ground state manifold into the A′5B2 and B5A1 states, which we model with multi-reference quantum chemical calculations including spin–orbit coupling. The calculations show that these transitions are symmetry forbidden in FeH+ and in the equilibrium geometry of ArFeH+/ArFeD+, while the zero-point oscillation of the bending mode of the triatomic molecule leads to some oscillator strength. Upon addition of the second argon atom, the transitions become weakly allowed in the equilibrium geometry of Ar2FeH+/Ar2FeD+ due to symmetry reduction from C∞v to C2v. [ABSTRACT FROM AUTHOR]

As one of the main components of sea salt aerosols, sodium chloride is involved in numerous atmospheric processes. Gas-phase clusters are ideal models to study fundamental physical and chemical properties of sodium chloride, which are significantly affected by the cluster size. Of particular interest are magic cluster sizes, which exhibit high intensities in mass spectra. In order to understand the origin of these magic cluster sizes, quantum chemical calculations at the CCSD(T)//DFT level are performed, yielding structures and binding energies of neutral (NaCl)x, anionic (NaCl)xCl− and cationic (NaCl)xNa+ clusters up to x = 8. Our calculations show that the clusters can easily isomerize, enabling dissociation into the lowest-energy isomers of the fragments. Energetics can explain the special stability of (NaCl)4Cl−, but (NaCl)4Na+ actually offers low-lying dissociation channels, despite being a magic cluster size. Collision-induced dissociation experiments reveal that the loss of neutral clusters (NaCl)x, x = 2, 4, is in most cases more favorable than the loss of NaCl or the atomic ion, i.e. sodium chloride clusters actually fragment via the cleavage of the entire cluster, not by evaporating small cluster building blocks. This is rationalized by the calculated high stability of even-numbered neutral clusters (NaCl)x, especially x = 2, 4. Analysis of the density of states and rate constants calculated with a modified Rice–Ramsperger–Kassel–Marcus (RRKM) equation called AWATAR – considering all energetically accessible isomers of reactants and fragments – shows that entropic effects are responsible for the magic cluster character of (NaCl)4Na+. In particular, low-lying vibrational modes provide a high density of states of the near-planar cluster. Together with the small contribution of an atomic ion to the sum of states in a loose transition state for dissociation, this leads to a very small unimolecular rate constant for dissociation into (NaCl)4 and Na+, which is the lowest energy fragmentation pathway. Thus, entropic effects may override energetics for certain magic cluster sizes. [ABSTRACT FROM AUTHOR]

Proton transfer reaction mass spectrometry has a so far little exploited potential for the analysis of high-purity process and inert gases. In order to protonate impurities like saturated hydrocarbons, precursor ions with very low proton affinity must be used, which in turn leads to a large energy release upon protonation of molecules with high proton affinity, potentially causing fragmentation of the product ions. To explore the potential of low-proton affinity precursor ions like ArH+ and N2H+ for analytical purposes, we studied their gas-phase reactions and kinetics with acetone by Fourier transform ion cyclotron resonance (FT–ICR) mass spectrometry. The dominant product ion in both cases is protonated acetone, but fragment ions formed include C2H3O+, C3H5+ and CH3O+, which are formed in higher abundance with ArH+ compared to N2H+. The reaction efficiencies are determined to be close to 100%. Quantum chemical calculations reveal energetically favorable reaction pathways and explain the loss of water leading to the formation of C3H5+, as well as loss of methane to yield C2H3O+via dissociative proton attachment, which corresponds to the main product in the EI mass spectrum of acetone. Formation of protonated formaldehyde CH3O+ involves rearrangement of the C–C bonds to eliminate ethylene. [ABSTRACT FROM AUTHOR]

Hydrated molecular anions are present in the atmosphere. Revealing the structure of the microsolvation is key to understanding their chemical properties. The infrared spectra of CO3•−(H2O)1,2 and CO4•−(H2O)1,2 were measured via infrared multiple photon dissociation spectroscopy in both warm and cold environments. Redshifted from the free O–H stretch frequency, broad, structured spectra were observed in the O–H stretching region for all cluster ions, which provide information on the interaction of the hydrogen atoms with the central ion. In the C–O stretching region, the spectra exhibit clear maxima, but dissociation of CO3•−(H2O)1,2 was surprisingly inefficient. While CO3•−(H2O)1,2 and CO4•−(H2O) dissociate via loss of water, CO2 loss is the dominant dissociation channel for CO4•−(H2O)2. The experimental spectra are compared to calculated spectra within the harmonic approximation and from analysis of molecular dynamics simulations. The simulations support the hypothesis that many isomers contribute to the observed spectrum at finite temperatures. The highly fluxional nature of the clusters is the main reason for the spectral broadening, while water–water hydrogen bonding seems to play a minor role in the doubly hydrated species. [ABSTRACT FROM AUTHOR]

We investigate the structure of copper formate and deuterated copper formate clusters using infrared multiple photon dissociation in combination with quantum chemical calculations. Symmetric and asymmetric C–O stretching vibrations along with C–H/C–D stretching vibrations were characterized. Fermi interactions between the C–H stretch and likely a C–O combination band and/or the overtone of a C–H in-plane bending motion have been confirmed by deuteration. The spectra reveal a strong dependence on the monodentate or bidentate binding motif of the formate ligands. Many minima are energetically accessible on the potential energy surface through rotation of the monodentate formate ligands into several almost isoenergetic local minima. While the C–H/C–D stretching vibration is heavily influenced by the charge distribution in the cluster, the C–O vibrations are largely unaffected. The C–H stretch region is not very diagnostic due to a variety of possible Fermi resonances, which also depend on the charge distribution at the formate ligand. Deuteration yields unperturbed spectra in the C–D stretch region and reveals characteristic shifts of the C–D stretching mode for the different binding motifs, with a strong dependence of the band position on the oxidation state of the copper center. The observed bands are compared with formate adsorbed on copper surfaces from the literature. [ABSTRACT FROM AUTHOR]

Proton transfer reactions (PTR) are important for chemical ionization, especially in trace gas analysis in air. In an effort to extend their application to the analysis of high‐purity inert gases, we studied PTR of N2H+ and ArH+ with various reaction gases, viz. O2, N2, CH4, CO2, NO2, H2O and CH3OH. Oxygen, nitrogen, methane, carbon dioxide, and water undergo non‐dissociative proton transfer, where the original molecule remains intact. PTR to nitrogen dioxide leads to NO+ with release of neutral OH⋅. While PTR from N2H+ to methanol exclusively yields protonated methanol, the reaction with ArH+ exhibits dissociative proton transfer, due to its higher exothermicity. Products include methenium, protonated formaldehyde, and protonated methanol. The latter undergoes a slow secondary reaction to form protonated dimethyl ether. Within error limits, most reactions proceed at or close to collision rate. Quantum chemical calculations provide energetics and reaction pathways. In such highly exothermic proton transfer reactions, identification and quantification of trace compounds require detailed understanding of the fragmentation pathways and branching ratios. [ABSTRACT FROM AUTHOR]

A versatile multifunctional laboratory-based near ambient pressure x-ray photoelectron spectroscopy (XPS) instrument is presented. The entire device is highly customized regarding geometry, exchangeable manipulators and sample stages for liquid- and solid-state electrochemistry, cryochemistry, and heterogeneous catalysis. It therefore delivers novel and unique access to a variety of experimental approaches toward a broad choice of functional materials and their specific surface processes. The high-temperature (electro)catalysis manipulator is designed for probing solid state/gas phase interactions for heterogeneous catalysts including solid electrolyzer/fuel cell electrocatalysts at pressures up to 15 mbar and temperatures from room temperature to 1000 °C. The liquid electrochemistry manipulator is specifically designed for in situ spectroscopic investigations of polarized solid/liquid interfaces using aqueous electrolytes and the third one for experiments for ice and ice-like materials at cryogenic temperatures to approximately −190 °C. The flexible and modular combination of these setups provides the opportunity to address a broad spectrum of in situ and operando XPS experiments on a laboratory-based system, circumventing the limited accessibility of experiments at synchrotron facilities. [ABSTRACT FROM AUTHOR]