Multiconfigurational Character of Repulsive A2Σg+ State Leaves Strong Signature in the Photodissociation Spectrum of Zn2.

For the excitation to a repulsive state of a diatomic molecule, one expects a single broad peak in the photodissociation spectrum. For Zn2+, however, two peaks for the spin- and symmetry-allowed A2Σg+ ← X2Σu+ transition are observed. A detailed quantum-chemical analysis reveals pronounced multiconfigurational character of the A2Σg+ state. The σg(4s)2σg(4p) configuration with bond order 1.5 dominates at short distances, while the repulsive σg(4s)σu*(4s)2 configuration with bond order -0.5 wins over with increasing bond length. The two excited-state configurations contribute with opposite signs to the transition dipole moment, which reaches zero near the equilibrium distance. This local minimum of the oscillator strength is responsible for the pronounced dip in the photodissociation spectrum, which is thus the spectroscopic signature of the multiconfigurational character of the A2Σg+ state.

Magic cluster sizes of cationic and anionic sodium chloride clusters explained by statistical modeling of the complete phase space.

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.

Iron Complexes as Potential Carriers of Diffuse Interstellar Bands: The Photodissociation Spectrum of Fe+(H2O) at Optical Wavelengths.

The fullerene ion C60+ is the only carrier of diffuse interstellar bands (DIBs) identified so far. Transition-metal compounds feature electronic transitions in the visible and near-infrared regions, making them potential DIB carriers. Since iron is the most abundant transition metal in the cosmos, we here test this idea with Fe+(H2O). Laboratory spectra were obtained by photodissociation spectroscopy at 80 K. Spectra were modeled with the reflection principle. A high-resolution spectrum of the DIB standard star HD 183143 served as an observational reference. Two broad bands were observed from 4120 to 6800 Å. The 4120-4800 Å band has sharp features emerging from the background, which have the width of DIBs but do not match the band positions of the reference spectrum. Calculations show that the spectrum arises from a d-d transition at the iron center. While no match was found for Fe+(H2O) with known DIBs, the observation of structured bands with line widths typical for DIBs shows that small molecules or molecular ions containing iron are promising candidates for DIB carriers.

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions.

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.

Thermally Activated vs. Photochemical Hydrogen Evolution Reactions-A Tale of Three Metals.

Molecular processes behind hydrogen evolution reactions can be quite complex. In macroscopic electrochemical cells, it is extremely difficult to elucidate and understand their mechanism. Gas phase models, consisting of a metal ion and a small number of water molecules, provide unique opportunities to understand the reaction pathways in great detail. Hydrogen evolution in clusters consisting of a singly charged metal ion and one to on the order of 50 water molecules has been studied extensively for magnesium, aluminum and vanadium. Such clusters with around 10-20 water molecules are known to eliminate atomic or molecular hydrogen upon mild activation by room temperature black-body radiation. Irradiation with ultraviolet light, by contrast, enables hydrogen evolution already with a single water molecule. Here, we analyze and compare the reaction mechanisms for hydrogen evolution on the ground state as well as excited state potential energy surfaces. Five distinct mechanisms for evolution of atomic or molecular hydrogen are identified and characterized.

Carbon Dioxide and Water Activation by Niobium Trioxide Anions in the Gas Phase.

Transition metals are important in various industrial applications including catalysis. Due to the current concentration of CO2 in the atmosphere, various ways for its capture and utilization are investigated. Here, we study the activation of CO2 and H2O at [NbO3]- in the gas phase using a combination of infrared multiple photon dissociation spectroscopy and density functional theory calculations. In the experiments, Fourier-transform ion cyclotron resonance mass spectrometry is combined with tunable IR laser light provided by the intracavity free-electron laser FELICE or optical parametric oscillator-based table-top laser systems. We present spectra of [NbO3]-, [NbO2(OH)2]-, [NbO2(OH)2]-(H2O) and [NbO(OH)2(CO3)]- in the 240-4000 cm-1 range. The measured spectra and observed dissociation channels together with quantum chemical calculations confirm that upon interaction with a water molecule, [NbO3]- is transformed to [NbO2(OH)2]- via a barrierless reaction. Reaction of this product with CO2 leads to [NbO(OH)2(CO3)]- with the formation of a [CO3] moiety.

Simplified Multiple-Well Approach for the Master Equation Modeling of Blackbody Infrared Radiative Dissociation of Hydrated Carbonate Radical Anions.

Blackbody infrared radiative dissociation (BIRD) in a collision-free environment is a powerful method for the experimental determination of bond dissociation energies. In this work, we investigate temperature-dependent BIRD of CO3·-(H2O)1,2 at 250-330 K to determine water binding energies and assess the influence of multiple isomers on the dissociation kinetics. The ions are trapped in a Fourier-transform ion cyclotron resonance mass spectrometer, mass selected, and their BIRD kinetics are recorded at varying temperatures. Experimental BIRD rates as a function of temperature are fitted with rates obtained from master equation modeling (MEM), using the water binding energy as a fit parameter. MEM accounts for the absorption and emission of photons from black-body radiation, described with harmonic frequencies and infrared intensities from quantum chemical calculations. The dissociation rates as a function of internal energy are calculated by Rice-Ramsperger-Kassel-Marcus theory. Both single-well and multiple-well MEM approaches are used. Dissociation energies derived in this way from the experimental data are 56 ± 6 and 45 ± 3 kJ/mol for the first and second water molecules, respectively. They agree within error limits with the ones predicted by ab initio calculations done at the CCSD(T)/aug-cc-pVQZ//CCSD/aug-cc-pVDZ level of theory. We show that the multiple-well MEM approach described here yields superior results in systems with several low-lying minima, which is the typical situation for hydrated ions.

Formation of Temporary Negative Ions and Their Subsequent Fragmentation upon Electron Attachment to CoQ0 and CoQ0 H2.

Ubiquinone molecules have a high biological relevance due to their action as electron carriers in the mitochondrial electron transport chain. Here, we studied the dissociative interaction of free electrons with CoQ0 , the smallest ubiquinone derivative with no isoprenyl units, and its fully reduced form, 2,3-dimethoxy-5-methylhydroquinone (CoQ0 H2 ), an ubiquinol derivative. The anionic products produced upon dissociative electron attachment (DEA) were detected by quadrupole mass spectrometry and studied theoretically through quantum chemical and electron scattering calculations. Despite the structural similarity of the two studied molecules, remarkably only a few DEA reactions are present for both compounds, such as abstraction of a neutral hydrogen atom or the release of a negatively charged methyl group. While the loss of a neutral methyl group represents the most abundant reaction observed in DEA to CoQ0 , this pathway is not observed for CoQ0 H2 . Instead, the loss of a neutral OH radical from the CoQ0 H2 temporary negative ion is observed as the most abundant reaction channel. Overall, this study gives insights into electron attachment properties of simple derivatives of more complex molecules found in biochemical pathways.

Size-dependent H and H2 formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations, V+(H2O)n, n = 3-51.

Infrared spectra of the hydrated vanadium cation (V+(H2O)n; n = 3-51) were measured in the O-H stretching region employing infrared multiple photon dissociation (IRMPD) spectroscopy. Spectral fingerprints, along with size-dependent fragmentation channels, were observed and rationalized by comparing to spectra simulated using density functional theory. Photodissociation leading to water loss was found for cluster sizes n = 3-7, consistent with isomers featuring intact water ligands. Loss of molecular hydrogen was observed as a weak channel starting at n = 8, indicating the advent of inserted isomers, HVOH+(H2O)n-1. The majority of ions for n = 8, however, are composed of two-dimensional intact isomers, concordant with previous infrared studies on hydrated vanadium. A third channel, loss of atomic hydrogen, is observed weakly for n = 9-11, coinciding with the point at which the H and H2O calculated binding energies become energetically competitive for intact isomers. A clear and sudden spectral pattern and fragmentation channel intensity at n = 12 suggest a structural change to inserted isomers. The H2 channel intensity decreases sharply and is not observed for n = 20 and 25-51. IRMPD spectra for clusters sizes n = 15-51 are qualitatively similar indicating no significant structural changes, and are thought to be composed of inserted isomers, consistent with recent electronic spectroscopy experiments.

Rearrangement and decomposition pathways of bare and hydrogenated molybdenum oxysulfides in the gas phase.

Molybdenum sulfides and molybdenum oxysulfides are considered a promising and cheap alternative to platinum as a catalyst for the hydrogen evolution reaction (HER). To better understand possible rearrangements during catalyst activation, we perform collision induced dissociation experiments in the gas phase with eight different molybdenum oxysulfides, namely [Mo2O2S6]2-, [Mo2O2S6]-, [Mo2O2S5]2-, [Mo2O2S5]-, [Mo2O2S4]-, [HMo2O2S6]-, [HMo2O2S5]- and [HMo2O2S4]-, on a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. We identify fragmentation channels of the molybdenum oxysulfides and their interconnections. Together with quantum chemical calculations, the results show that [Mo2O2S4]- is a particularly stable species against further dissociation, which is reached from all starting species with relatively low collision energies. Most interestingly, H atom loss is the only fragmentation channel observed for [HMo2O2S4]- at low collision energies, which relates to potential HER activity, since two such H atom binding sites on a surface may act together to release H2. The calculations reveal that multiple isomers are often very close in energy, especially for the hydrogenated species, i.e., atomic hydrogen can bind at various sites of the clusters. S2 groups play a decisive role in hydrogen adsorption. These are further features with potential relevance for HER catalysis.

Photochemical Hydrogen Evolution at Metal Centers Probed with Hydrated Aluminium Cations, Al+ (H2 O)n , n=1-10.

Hydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s-3p excitations of Al+ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S1 to T2 takes place, and photochemical hydrogen formation starts on the T2 surface, which passes through a conical intersection, changing to T1 . On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH+ (H2 O)n-1 and are transparent in the investigated energy range. For n=4-8, a mixture of Al+ (H2 O)n and HAlOH+ (H2 O)n-1 is present in the experiment.

Activation of a Copper Biscarbene Mechano-Catalyst Using Single-Molecule Force Spectroscopy Supported by Quantum Chemical Calculations.

Single-molecule force spectroscopy allows investigation of the effect of mechanical force on individual bonds. By determining the forces necessary to sufficiently activate bonds to trigger dissociation, it is possible to predict the behavior of mechanophores. The force necessary to activate a copper biscarbene mechano-catalyst intended for self-healing materials was measured. By using a safety line bypassing the mechanophore, it was possible to pinpoint the dissociation of the investigated bond and determine rupture forces to range from 1.6 to 2.6 nN at room temperature in dimethyl sulfoxide. The average length-increase upon rupture of the Cu-C bond, due to the stretching of the safety line, agrees with quantum chemical calculations, but the values exhibit an unusual scattering. This scattering was assigned to the conformational flexibility of the mechanophore, which includes formation of a threaded structure and recoiling of the safety line.

Spectroscopy and photochemistry of copper nitrate clusters.

The investigation of copper nitrate cluster anions Cu(ii)n(NO3)2n+1-, n ≤ 4, in the gas phase using ultraviolet/visible/near-infrared (UV/vis/NIR) spectroscopy provides detailed insight into the electronic structure of the copper salt and its intriguing photochemistry. In the experimentally studied region up to 5.5 eV, the spectra of copper(ii) nitrate exhibit a 3d-3d band in the vis/NIR and well-separated bands in the UV. The latter bands originate from Ligand-to-Metal Charge Transfer (LMCT) as well as n-π* transitions in the nitrate ligands. The clusters predominantly decompose by loss of neutral copper nitrate in the electronic ground state after internal conversion or via the photochemical loss of a neutral NO3 ligand after a LMCT. These two decomposition channels are in direct competition on the ground state potential energy surface for the smallest copper nitrate cluster, Cu(ii)(NO3)3-. Here, copper nitrate evaporation is thermochemically less favorable. Population of π* orbitals in the nitrate ligands may lead to N-O bond photolysis. This is observed in the UV region with a small quantum efficiency, with photochemical loss of either nitrogen dioxide or an oxygen atom.

Photochemistry and UV/vis spectroscopy of hydrated vanadium cations, V+(H2O)n, n = 1-41, a model system for photochemical hydrogen evolution.

Photochemical hydrogen evolution provides fascinating perspectives for light harvesting. Hydrated metal ions in the gas phase are ideal model systems to study elementary steps of this reaction on a molecular level. Here we investigate mass-selected hydrated monovalent vanadium ions, with a hydration shell ranging from 1 to 41 water molecules, by photodissociation spectroscopy. The most intense absorption bands correspond to 3d-4p transitions, which shift to the red from n = 1 to n = 4, corresponding to the evolution of a square-planar complex. Additional water molecules no longer interact directly with the metal center, and no strong systematic shift is observed in larger clusters. Evolution of atomic and molecular hydrogen competes with loss of water molecules for all V+(H2O)n, n ≤ 12. For n ≥ 15, no absorptions are observed, which indicates that the cluster ensemble is fully converted to HVOH+(H2O)n-1. For the smallest clusters, the electronic transitions are modeled using multireference methods with spin-orbit coupling. A large number of quintet and triplet states is accessible, which explains the broad features observed in the experiment. Water loss most likely occurs after a series of intersystem crossings and internal conversions to the electronic ground state or a low-lying quintet state, while hydrogen evolution is favored in low lying triplet states.

Microsolvation of Zn cations: infrared multiple photon dissociation spectroscopy of Zn+(H2O)n (n = 2-35).

The structures, along with solvation evolution, of size-selected Zn+(H2O)n (n = 2-35) complexes have been determined by combining infrared multiple photon photodissociation (IRMPD) spectroscopy and density functional theory. The infrared spectra were recorded in the O-H stretching region, revealing varying shifts in band position due to different water binding motifs. Concordant with previous studies, a coordination number of 3 is observed, determined by the sudden appearance of a broad, red-shifted band in the hydrogen bonding region for clusters n > 3. The coordination number of 3 seems to be retained even for the larger clusters, due to incoming ligands experiencing significant repulsion from the Zn+ valence 4s electron. Evidence of spectrally distinct single- and double-acceptor sites are presented for medium-sized clusters, 4 ≤n≤ 7, however for larger clusters, n≥ 8, the hydrogen bonding region is dominated by a broad, unresolved band, indicative of the increased number of second and third coordination sphere ligands. No evidence of a solvated, six-fold coordinated Zn2+ ion/solvated electron pair is present in the spectra.

Infrared spectroscopy of CO3 •-(H2O)1,2 and CO4 •-(H2O)1,2.

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.

Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1-20).

Investigating metal-ion solvation-in particular, the fundamental binding interactions-enhances the understanding of many processes, including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn2+(H2O)n; n = 1-20) were measured in the O-H stretching region, using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes, calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory, the spectra show that water molecules preferentially bind to one Zn atom, adopting water binding motifs similar to the Zn+(H2O)n complexes studied previously. A lower coordination number of 2 was observed for Zn2+(H2O)3, evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3, attributed to a particularly low calculated Zn binding energy for this cluster size.

[Mo3 S13 ]2- as a Model System for Hydrogen Evolution Catalysis by MoSx : Probing Protonation Sites in the Gas Phase by Infrared Multiple Photon Dissociation Spectroscopy.

Materials based on molybdenum sulfide are known as efficient hydrogen evolution reaction (HER) catalysts. As the binding site for H atoms on molybdenum sulfides for the catalytic process is under debate, [HMo3 S13 ]- is an interesting molecular model system to address this question. Herein, we probe the [HMo3 S13 ]- cluster in the gas phase by coupling Fourier-transform ion-cyclotron-resonance mass spectrometry (FT-ICR MS) with infrared multiple photon dissociation (IRMPD) spectroscopy. Our investigations show one distinct S-H stretching vibration at 2450 cm-1 . Thermochemical arguments based on DFT calculations strongly suggest a terminal disulfide unit as the H adsorption site.

Getting Ready for the Hydrogen Evolution Reaction: The Infrared Spectrum of Hydrated Aluminum Hydride-Hydroxide HAlOH+ (H2 O)n-1 , n=9-14.

Hydrated singly charged aluminum ions eliminate molecular hydrogen in a size regime from 11 to 24 water molecules. Here we probe the structure of HAlOH+ (H2 O)n-1 , n=9-14, by infrared multiple photon spectroscopy in the region of 1400-2250 cm-1 . Based on quantum chemical calculations, we assign the features at 1940 cm-1 and 1850 cm-1 to the Al-H stretch in five- and six-coordinate aluminum(III) complexes, respectively. Hydrogen bonding towards the hydride is observed, starting at n=12. The frequency of the Al-H stretch is very sensitive to the structure of the hydrogen bonding network, and the large number of isomers leads to significant broadening and red-shifting of the absorption of the hydrogen-bonded Al-H stretch. The hydride can even act as a double hydrogen bond acceptor, shifting the Al-H stretch to frequencies below those of the water bending mode. The onset of hydrogen bonding and disappearance of the free Al-H stretch coincides with the onset of hydrogen evolution.

Chemistry of NOx and HNO3 Molecules with Gas-Phase Hydrated O.- and OH- Ions.

The gas-phase reactions of O. - (H2 O)n and OH- (H2 O)n , n=20-38, with nitrogen-containing atmospherically relevant molecules, namely NOx and HNO3 , are studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and theoretically with the use of DFT calculations. Hydrated O. - anions oxidize NO. and NO2 . to NO2 - and NO3 - through a strongly exothermic reaction with enthalpy of -263±47 kJ mol-1 and -286±42 kJ mol-1 , indicating a covalent bond formation. Comparison of the rate coefficients with collision models shows that the reactions are kinetically slow with 3.3 and 6.5 % collision efficiency. Reactions between hydrated OH- anions and nitric oxides were not observed in the present experiment and are most likely thermodynamically hindered. In contrast, both hydrated anions are reactive toward HNO3 through proton transfer from nitric acid, yielding hydrated NO3 - . Although HNO3 is efficiently picked-up by the water clusters, forming (HNO3 )0-2 (H2 O)m NO3 - clusters, the overall kinetics of nitrate formation are slow and correspond to an efficiency below 10 %. Combination of the measured reaction thermochemistry with literature values in thermochemical cycles yields ΔHf (O- (aq.))=48±42 kJ mol-1 and ΔHf (NO2 - (aq.))=-125±63 kJ mol-1 .