Establishing the structural motifs present in small ammonium and aminium bisulfate clusters of relevance to atmospheric new particle formation.

Atmospheric new particle formation is the process by which atmospheric trace gases, typically acids and bases, cluster and grow into potentially climatically relevant particles. Here, we evaluate the structures and structural motifs present in small cationic ammonium and aminium bisulfate clusters that have been studied both experimentally and computationally as seeds for new particles. For several previously studied clusters, multiple different minimum-energy structures have been predicted. Vibrational spectra of mass-selected clusters and quantum chemical calculations allow us to assign the minimum-energy structure for the smallest cationic cluster of two ammonium ions and one bisulfate ion to a CS-symmetry structure that is persistent under amine substitution. We derive phenomenological vibrational frequency scaling factors for key bisulfate vibrations to aid in the comparison of experimental and computed spectra of larger clusters. Finally, we identify a previously unassigned spectral marker for intermolecular bisulfate-bisulfate hydrogen bonds and show that it is present in a class of structures that are all lower in energy than any previously reported structure. Tracking this marker suggests that this motif is prominent in larger clusters as well as ∼180 nm ammonium bisulfate particles. Taken together, these results establish a set of structural motifs responsible for binding of gases at the surface of growing clusters that fully explain the spectrum of large particles and provide benchmarks for efforts to improve structure predictions, which are critical for the accurate theoretical treatment of this process.

Electrospray Ionization-Based Synthesis and Validation of Amine-Sulfuric Acid Clusters of Relevance to Atmospheric New Particle Formation.

Atmospheric new particle formation (NPF) is the process by which atmospheric trace gases such as sulfuric acid, ammonia, and amines cluster and grow into climatically relevant particles. The mechanism by which these particles form and grow has remained unclear, in large part due to difficulties in obtaining molecular-level information about the clusters as they grow. Mass spectrometry-based methods using electrospray ionization (ESI) as a cluster source have shed light on this process, but the produced cluster distributions have not been rigorously validated against experiments performed in atmospheric conditions. Ionic clusters are produced by ESI of solutions containing the amine and bisulfate or by spraying a sulfuric acid solution and introducing trace amounts of amine gas into the ESI environment. The amine content of clusters can be altered by increasing the amount of amine introduced into the ESI environment, and certain cluster compositions can only be made by the vapor exchange method. Both approaches are found to yield clusters with the same structures. Aminium bisulfate cluster distributions produced in a controlled and isolated ESI environment can be optimized to closely resemble those observed by chemical ionization in the CLOUD chamber at CERN. These studies indicate that clusters generated by ESI are also observed in traditional atmospheric measurements, which puts ESI mass spectrometry-based studies on firmer footing and broadens the scope of traditional mass spectrometry experiments that may be applied to NPF.

Chemical Ionization Mass Spectrometry: Applications for the In Situ Measurement of Nonvolatile Organics at Ocean Worlds.

A new technique that has applications for the detection of nonvolatile organics on Ocean Worlds has been developed. Here, liquid mixtures of fatty acids (FAs) and/or amino acids (AAs) are introduced directly into a miniature quadrupole ion trap mass spectrometer (QITMS) developed at Jet Propulsion Laboratory and analyzed. Two ionization methods, electron impact and chemical ionization (EI and CI, respectively), are compared and contrasted. Further, multiple CI reagents are tested to explore their potential to "soften" ionization of FAs and AAs. Both EI and CI yield mass spectra that bear signatures of FAs or AAs; however, soft CI yields significantly cleaner mass spectra that are easier to interpret. The combination of soft CI with tandem mass spectrometry (MS/MS) has also been demonstrated for AAs, generating "fingerprint" mass spectra of fragments from protonated parent ions. To mimic potential Ocean World conditions, water is used as the primary collision gas in MS/MS experiments. This technique has the potential for the in situ analysis of molecules in the cryogenic plumes of Ocean Worlds (e.g., Enceladus) and comets with the ultimate goal of detecting potential biosignatures.

Direct Link between Structure and Hydration in Ammonium and Aminium Bisulfate Clusters Implicated in Atmospheric New Particle Formation.

The acid-base chemistry of amines and sulfuric acid promotes growth in the early stages of atmospheric new particle formation, with more basic amines enhancing growth rates. Hydration of these particles has been proposed to depend on acidity or basicity but is difficult to quantify; therefore, the role of water in this process is not well understood. Using tandem mass spectrometry coupled to a temperature-controlled ion trap, we show that water uptake by aminium bisulfate clusters depends on the total number of free hydrogen bond donors in the cluster and is unaffected by the interchange of amines featuring the same number of substituents but differing gas-phase basicity. Analyzing this trend reveals site-specific propensities for hydration. These results indicate that hydration is determined by structural factors and that reported dependences on acidity or basicity arise from the weaker correlation between the number of hydrogen bond donors of amines and their gas-phase basicity.

The Interplay Between Hydrogen Bonding and Coulombic Forces in Determining the Structure of Sulfuric Acid-Amine Clusters.

Acid-base cluster chemistry drives atmospheric new particle formation (NPF), but the details of the growth mechanisms are difficult to experimentally probe. Clusters of ammonia, alkylamines, and sulfuric acid, species fundamental to NPF, are probed by infrared spectroscopy. These spectra show that substitution of amines for ammonia, which is linked to accelerated growth, induces profound structural rearrangement in clusters with initial compositions (NH4+) n+1(HSO4-) n (1 ≤ n ≤ 3). This rearrangement is driven by the loss of N-H hydrogen bond donors, yielding direct bisulfate-bisulfate hydrogen bonds, and its onset with respect to cluster composition indicates that more substituted amines induce rearrangement at smaller sizes. A simple model counting hydrogen bond donors and acceptors explains these observations. The presence of direct hydrogen bonds between formal anions shows that hydrogen bonding can compete with Coulombic forces in determining cluster structure. These results suggest that NPF mechanisms may be highly dependent on amine identity.

Effect of Alkyl Group on MxOy(-) + ROH (M = Mo, W; R = Me, Et) Reaction Rates.

A systematic comparison of MxOy(-) + ROH (M = Mo vs W; R = Me vs Et) reaction rate coefficients and product distributions combined with results of calculations on weakly bound MxOy(-)·ROH complexes suggest that the overall reaction mechanism has three distinct steps, consistent with recently reported results on analogous MxOy(-) + H2O reactivity studies. MxOy(-) + ROH → MxOy+1(-) + RH oxidation reactions are observed for the least oxidized clusters, and MxOy(-) + ROH → MxOyROH(-) addition reactions are observed for clusters in intermediate oxidation states, as observed previously in MxOy(-) + H2O reactions. The first step is weakly bound complex formation, the rate of which is governed by the relative stability of the MxOy(-)·ROH charge-dipole complexes and the Lewis acid-base complexes. Calculations predict that MoxOy(-) clusters form more stable Lewis acid-base complexes than WxOy(-), and the stability of EtOH complexes is enhanced relative to MeOH. Consistent with this result, MoxOy(-) + ROH rate coefficients are higher than analogous WxOy(-) clusters. Rate coefficients range from 2.7 × 10(-13) cm(3) s(-1) for W3O8(-) + MeOH to 3.4 × 10(-11) cm(3) s(-1) for Mo2O4(-) + EtOH. Second, a covalently bound complex is formed, and anion photoelectron spectra of the several MxOyROH(-) addition products observed are consistent with hydroxyl-alkoxy structures that are formed readily from the Lewis acid-base complexes. Calculations indicate that addition products are trapped intermediates in the MxOy(-) + ROH → MxOy+1(-) + RH reaction, and the third step is rearrangement of the hydroxyl group to a metal hydride group to facilitate RH release. Trapped intermediates are more prevalent in MoxOy(-) reaction product distributions, indicating that the rate of this step is higher for WxOy+1RH(-) than for MoxOy+1RH(-). This result is consistent with previous computational studies on analogous MxOy(-) + H2O reactions predicting that barriers along the pathway in the rearrangement step are higher for MoxOy(-) reactions than for WxOy(-).

Ce(x)O(y)⁻ (x = 2-3) + D2O reactions: stoichiometric cluster formation from deuteroxide decomposition and anti-Arrhenius behavior.

Reactions between small cerium oxide cluster anions and deuterated water were monitored as a function of both water concentration and temperature in order to determine the temperature dependence of the rate constants. Sequential oxidation reactions of the Ce(x)O(y)⁻ (x = 2, 3) suboxide cluster anions were found to exhibit anti-Arrhenius behavior, with activation energies ranging from 0 to -18 kJ mol⁻¹. Direct oxidation of species up to y = x was observed, after which, -OD abstraction and D2O addition reactions were observed. However, the stoichiometric Ce2O4⁻ and Ce3O6⁻ cluster anions also emerge in reactions between D2O and the respective precursors, Ce2O3D⁻ and Ce3O5D2⁻. Ce2O4⁻ and Ce3O6⁻ product intensities diminish relative to deuteroxide complex intensities with increasing temperature. The kinetics of these reactions are compared to the kinetics of the previously studied Mo(x)O(y)⁻ and W(x)O(y)⁻ reactions with water, and the possible implications for the reaction mechanisms are discussed.

Comparative study of water reactivity with Mo2O(y)⁻ and W2O(y)⁻ clusters: a combined experimental and theoretical investigation.

A computational investigation of the Mo2O(y)(-) + H2O (y = 4, 5) reactions as well as a photoelectron spectroscopic probe of the deuterated Mo2O6D2(-) product have been carried out to understand a puzzling question from a previous study: Why is the rate constant determined for the Mo2O5(-) + H2O/D2O reaction, the terminal reaction in the sequential oxidation of Mo2O(y)(-) by water, higher than the W2O5(-) + H2O/D2O reaction? This disparity was intriguing because W3O(y)(-) clusters were found to be more reactive toward water than their Mo3O(y)(-) analogs. A comparison of molecular structures reveals that the lowest energy structure of Mo2O5(-) provides a less hindered water addition site than the W2O5(-) ground state structure. Several modes of water addition to the most stable molecular and electronic structures of Mo2O4(-) and Mo2O5(-) were explored computationally. The various modes are discussed and compared with previous computational studies on W2O(y)(-) + H2O reactions. Calculated free energy reaction profiles show lower barriers for the initial Mo2O(y)(-) + H2O addition, consistent with the higher observed rate constant. The terminal Mo2O(y)(-) sequential oxidation product predicted computationally was verified by the anion photoelectron spectrum of Mo2O6D2(-). Based on the computational results, this anion is a trapped dihydroxide intermediate in the Mo2O5(-) + H2O/D2O → Mo2O6(-) + H2/D2 reaction.

RH and H2 production in reactions between ROH and small molybdenum oxide cluster anions.

To test recent computational studies on the mechanism of metal oxide cluster anion reactions with water [Ramabhadran, R. O.; et al. J. Phys. Chem. Lett. 2010, 1, 3066; Ramabhadran, R. O.; et al. J. Am. Chem. Soc. 2013, 135, 17039], the reactivity of molybdenum oxo­cluster anions, Mo(x)O(y)(­) (x = 1 ­ 4; y ≤ 3x) toward both methanol (MeOH) and ethanol (EtOH) has been studied using mass spectrometric analysis of products formed in a high-pressure, fast-flow reactor. The size-dependent product distributions are compared to previous Mo(x)O(y)(­) + H2O/D2O reactivity studies, with particular emphasis on the Mo2O(y)(­) and Mo3O(y)(­) series. In general, sequential oxidation, Mo(x)O(y)(­) + ROH → Mo(x)O(y+1)(­) + RH, and addition reactions, Mo(x)O(y)(­) + ROH → Mo(x)O(y+1)RH(­), largely corresponded with previously studied Mo(x)O(y)(­) + H2O/D2O reactions [Rothgeb, D. W., Mann, J. E., and Jarrold, C. C. J. Chem. Phys. 2010, 133, 054305], though with much lower rate constants than those determined for Mo(x)O(y)(­) + H2O/D2O reactions. This finding is consistent with the computational studies that suggested that −H mobility on the cluster­water complex was an important feature in the overall reactivity. There were several notable differences between cluster­ROH and cluster­water reactions associated with lower R­OH bond dissociation energies relative to the HO­H dissociation energy.

New insights on photocatalytic H2 liberation from water using transition-metal oxides: lessons from cluster models of molybdenum and tungsten oxides.

Molecular hydrogen (H2) is an excellent alternative fuel. It can be produced from the abundantly present water on earth. Transition-metal oxides are widely used in the environmentally benign photocatalytic generation of H2 from water, thus actively driving scientific research on the mechanisms for this process. In this study, we investigate the chemical reactions of W3O5(-) and Mo3O5(-) clusters with water that shed light on a variety of key factors central to H2 generation. Our computational results explain why experimentally Mo3O5(-) forms a unique kinetic trap in its reaction while W3O5(-) undergoes a facile oxidation to form the lowest-energy isomer of W3O6(-) and liberates H2. Mechanistic insights on the reaction pathways that occur, as well as the reaction pathways that do not occur, are found to be of immense assistance to comprehend the hitherto poorly understood pivotal roles of (a) differing metal-oxygen and metal-hydrogen bond strengths, (b) the initial electrostatic complex formed, (c) the loss of entropy when these TMO clusters react with water, and (d) the geometric factors involved in the liberation of H2.

Simple relationship between oxidation state and electron affinity in gas-phase metal-oxo complexes.

The photoelectron spectra of WO3H(-) and WO2F(-) are presented and analyzed in the context of a series of previous similar measurements on MO(y)(-) (M = Mo, W; y = 0-3), MO4H(-) and AlMOy(-) (y ≤ 4) complexes. The electronic structures of the WO3H and WO2F anion and neutral complexes were investigated using the B3LYP hybrid density functional method. The spectra of WO3H(-), WO2F(-), and previously measured AlWO3(-) photoelectron spectra show that the corresponding neutrals, in which the transition metal centers are all in a +5 oxidation state, have comparable electron affinities. In addition, the electron affinities fit the general trend of monotonically increasing electron affinity with oxidation state, in spite of the WO3H(-), WO2F(-), and AlWO3(-) having closed shell ground states, suggesting that the oxidation state of the metal atom has more influence than shell closing on the electron affinity of these transition metal-oxo complexes. Results of DFT calculations suggest that the neutrals are pyramidal and the anions are planar. However, the barriers for inversion on the neutral surface are low, and attempts to generate simple Franck-Condon simulations based on simple normal coordinate displacement, ignoring the effects of inversion, are inadequate.

Shift from covalent to ionic bonding in Al2MoO(y) (y = 2-4) anion and neutral clusters.

The electronic and molecular structures of Al2MoO(y) (y = 2-4) anion and neutral complexes were studied using anion photoelectron spectroscopy and density functional theory calculations. The spectra are broad, reflecting significant structural changes in the transition from anion to neutral, and the neutral electron affinities determined from the spectra are similar for all three species. The calculations suggest that the lowest energy isomers of the neutral clusters can be described as predominantly (Al(+))2[MoO(y)(-2)] ionic complexes, in which the Al(+) cations bond with O(2-) anions in a way that minimizes repulsion with the positively charged Mo center. The anion structures for all three complexes favor closer Mo-Al and Al-Al internuclear distances, with the extra negative charge distributed more evenly among all three metal centers. Energetically, the fully occupied 3s orbitals on the Al centers are lower than the Mo-local 4d-like orbitals and above the O-local 2p-like orbitals. In the case of Al2MoO2(-), there is direct Al-Al covalent bonding. The calculated spectroscopic parameters for these species are consistent with the observed spectra, though definitive assignments are not possible due to the broad, unresolved spectra observed and predicted.

Asymmetric partitioning of metals among cluster anions and cations generated via laser ablation of mixed aluminum/Group 6 transition metal targets.

While high-power laser ablation of metal alloys indiscriminately produces gas-phase atomic ions in proportion to the abundance of the various metals in the alloy, gas-phase ions produced by moderate-power laser ablation sources coupled with molecular beams are formed by more complicated mechanisms. A mass spectrometric study that directly compares the mass distributions of cluster anions and cations generated from laser ablation of pure aluminum, an aluminum/molybdenum mixed target, and an aluminum/tungsten mixed target is detailed. Mass spectra of anionic species generated from the mixed targets showed that both tungsten and molybdenum were in higher abundance in the negatively charged species than in the target material. Mass spectra of the cationic species showed primarily Al(+) and aluminum oxide and hydroxide cluster cations. No molybdenum- or tungsten-containing cluster cations were definitively assigned. The asymmetric distribution of aluminum and Group 6 transition metals in cation and anion cluster composition is attributed to the low ionization energy of atomic aluminum and aluminum suboxide clusters. In addition, the propensity of both molybdenum and tungsten to form metal oxide cluster anions under the same conditions that favor metallic aluminum cluster anions is attributed to differences in the optical properties of the surface oxide that is present in the metal powders used to prepare the ablation targets. Mechanisms of mixed metal oxide clusters are considered.

Study of MoNbO(y) (y = 2-5) anion and neutral clusters using photoelectron spectroscopy and density functional theory calculations: impact of spin contamination on single point calculations.

Results of a study combining anion photoelectron spectroscopy and density functional theory calculations on the heteronuclear MoNbO(y)(-) (y = 2-5) transition metal suboxide cluster series are reported and analyzed. The photoelectron spectra, which exhibit broad electronic bands with partially resolved vibrational structure, were compared to spectral simulations generated from calculated spectroscopic parameters for all computationally determined energetically competitive structures. Although computational results on the less oxidized clusters could not be satisfactorily reconciled with experimental spectra, possibly because of heavy spin contamination found in a large portion of the computational results, the results suggest that (1) neutral cluster electron affinity is a strong indicator of whether O-atoms are bound in M-O-M bridge positions or M═O terminal positions, (2) MoNbO(y) anions and neutrals have structures that can be described as intermediate with respect to the unary (homonuclear) Mo(2)O(y) and Nb(2)O(y) clusters, and (3) structures in which O-atoms preferentially bind to the Nb center are slightly more stable than alternative structures. Several challenges associated with the calculations are considered, including spin contamination, which appears to cause spurious single point calculations used to determine vertical detachment energies.

Electronic structures of WAlO(y) and WAlO(y)(-) (y = 2-4) determined by anion photoelectron spectroscopy and density functional theory calculations.

The anion photoelectron spectra of WAlO(y)(-) (y = 2-4) are presented and assigned based on results of density functional theory calculations. The WAlO(2)(-) and WAlO(3)(-) spectra are both broad, with partially resolved vibrational structure. In contrast, the WAlO(4)(-) spectrum features well-resolved vibrational structure with contributions from three modes. There is reasonable agreement between experiment and theory for all oxides, and calculations are in particular validated by the near perfect agreement between the WAlO(4)(-) photoelectron spectrum and a Franck-Condon simulation based on computationally determined spectroscopic parameters. The structures determined from this study suggest strong preferential W-O bond formation, and ionic bonding between Al(+) and WO(y)(-2) for all anions. Neutral species are similarly ionic, with WAlO(2) and WAlO(3) having electronic structure that suggests Al(+) ionically bound to WO(y)(-) and WAlO(4) being described as Al(+2) ionically bound to WO(4)(-2). The doubly-occupied 3sp hybrid orbital localized on the Al center is energetically situated between the bonding O-local molecular orbitals and the anti- or non-bonding W-local molecular orbitals. The structures determined in this study are very similar to structures recently determined for the analogous MoAlO(y)(-)/MoAlO(y) cluster series, with subtle differences found in the electronic structures [S. E. Waller, J. E. Mann, E. Hossain, M. Troyer, and C. C. Jarrold, J. Chem. Phys. 137, 024302 (2012)].

Electronic structures of AlMoO(y)(-) (y = 1-4) determined by photoelectron spectroscopy and density functional theory calculations.

Vibrationally-resolved photoelectron spectra of AlMoO(y)(-) (y = 1-4) are presented and analyzed in conjunction with density functional theory computational results. The structures determined for the AlMoO(y) anion and neutral clusters suggest ionic bonding between Al(+) and a MoO(y)(-) or MoO(y)(-2) moiety, and point to the relative stability of Mo=O versus Al=O bonds. The highest occupied and partially occupied orbitals in the anions and neutrals can be described as Mo atomic-like orbitals, so while the Mo is in a higher oxidation state than Al, the most energetically accessible electrons are localized on the molybdenum center.

Structures of trimetallic molybdenum and tungsten suboxide cluster anions.

Anion photoelectron spectra of Mo(3)O(y)(-) and W(3)O(y)(-) (y = 3-6) are reported and analyzed using density functional theory results in an attempt to determine whether electronic and structural trends in the less oxidized clusters (y = 3, 4) could elucidate the disparate chemical properties of the M(3)O(y)(-) (M = Mo, W, y = 5, 6) species. In general, cyclic structures are calculated to be more stable by at least 1 eV than extended structures, and the lowest energy structures calculated for the most reduced species favor M = O terminal bonds. While the numerous low-energy structures found for Mo(3)O(y)(-)/Mo(3)O(y) and W(3)O(y)(-)/W(3)O(y) were, in general, similar, various structures of W(3)O(y)(-)/W(3)O(y) were found to be energetically closer lying than analogous structures of Mo(3)O(y)(-)/Mo(3)O(y). Additionally, the Mo-O-Mo bridge bond was found to be a more stabilizing structural motif than the W-O-W bridge bond, with the oxygen center in the former having the highest negative charge. Based on this, the observation of trapped intermediates in reactions between Mo(3)O(y)(-) and water or CO(2) that are not observed in analogous W(3)O(y)(-) reactivity studies may be partially attributed to the role of bridge bond fluxionality.

Study of Nb2O(y) (y = 2-5) anion and neutral clusters using anion photoelectron spectroscopy and density functional theory calculations.

A study combining anion photoelectron spectroscopy and density functional theory calculations on the transition metal suboxide series, Nb(2)O(y)(-) (y = 2-5), is described. Photoelectron spectra of the clusters are obtained, and Franck-Condon simulations using calculated anion and neutral structures and frequencies are used to evaluate the calculations and assign transitions observed in the spectra. The spectra, several of which exhibit partially resolved vibrational structure, show an increase in electron affinity with increasing cluster oxidation state. Hole-burning experiments suggest that the photoelectron spectra of both Nb(2)O(2)(-) and Nb(2)O(3)(-) have contributions from more than one structural isomer. Reasonable agreement between experiment and computational results is found among all oxides.

Study of MoVO(y) (y = 2-5) anion and neutral clusters using anion photoelectron spectroscopy and density functional theory calculations.

The vibrationally resolved anion photoelectron (PE) spectra of MoVO(y)(-) (y = 2 - 5) metal suboxide clusters are presented and analyzed in the context of density functional theory (DFT) calculations. The electronically congested spectra reflect an increase in cluster electron affinity with increasing oxidation state. Ion beam hole-burning results reveal the features in the PE spectra of MoVO(2)(-) and MoVO(4)(-) are a result of only one anion isomer, while at least two isomers contribute to electronic structure observed in the PE spectrum of MoVO(3)(-). Spectral features of the binary systems are compared to their pure analogs, Mo(2)O(y) and V(2)O(y). An attempt to characterize the anion and neutral electronic and molecular structures is made by comparison with results from DFT calculations. However, reconciliation between the cluster spectra and the calculated spectroscopic parameters is not as straightforward as in previous studies on similar systems (Yoder, B. L.; Maze, J. T.; Raghavachari, K.; Jarrold, C. C. J. Chem. Phys. 2005, 122, 094313 and Mayhall, N. J.; Rothgeb, D. W.; Hossain, E.; Raghavachari, K.; Jarrold, C. C. J. Chem. Phys. 2009, 130, 124313).