Isomer-Dependent Electron Affinities of Fluorophenyl Radicals, •C6H5-xFx (2 ≤ x ≤ 4).

Di-, tri-, and tetrafluorophenyl radicals each have three regioisomers, several of which can form multiple distinct radical structures. We present the photoelectron spectra of the di-, tri-, and tetrafluorophenide regioisomer anions generated from their associated fluorobenzene precursors. By comparing the spectra to the results of density functional theory calculations, we determine that in cases where more than one possible radical isomer is possible for a given regioisomer (radicals formed from 1,2-difluorobenzene, 1,3-difluorobenzene, 1,2,3-trifluorobenzene, and 1,2,4-trifluorobenzene) the most stable anion corresponds to a less stable neutral, suggesting that the reactive C-center on these fluorine-substituted phenyl groups can be controlled by charge state. Full analyses of the spectra and computational results yield further insights into the differences between the electronic and molecular structures of the fluorophenyl radicals and their associated anions.

Anion Photoelectron Imaging Spectroscopy of C6HF5-, C6F6-, and the Absence of C6H2F4.

Substituents have a profound effect on the electronic structure of the benzene molecule. In this paper, we present new photoelectron spectra of the C5HF5- molecular anion, to test predictions [ Int. J. Quant. Chem. 2017, 188, e25504] that pentafluorobenzene has a positive electron affinity, as hexafluorobenzene was already known to have. The PE spectrum of C6HF5- exhibits a broad and vibrationally unresolved band due to significant differences between the structure of the anion and the neutral. The vertical detachment energy (VDE) of C5HF5- is determined to be 1.33 ± 0.05 eV, and the lowest binding energy at which the signal is observed is 0.53 ± 0.05 eV, which, if taken as the electron affinity, is in good agreement with the computed value. In addition, we attempted to generate intact C6H2F4- molecular ions using the 1,2,3,4-tetrafluorobenzene, 1,2,3,5-tetrafluorobenzene, and 1,2,4,5-tetrafluorobenzene precursors, as tetrafluorobenzene was predicted to have a near-zero but marginally positive electron affinity. Using a photoemission anion source, we were not able to produce the intact tetrafluorobenzene anion. Density functional theory calculations support a more detailed discussion of the impact of fluorine substitution on the electronic structure of these species.

Trend in the Electron Affinities of Fluorophenyl Radicals ·C6H5-xFx (1 ≤ x ≤ 4).

The electron affinities (EAs) of a series of ·C6H5-xFx (1 ≤ x ≤ 4) fluorophenyl radicals are determined from the photoelectron spectra of their associated fluorophenide anions generated from C6H6-xFx (1 ≤ x ≤ 4) fluorobenzene precursors. The spectra show a near-linear incremental increase in EA of 0.4 eV/x. The spectra exhibit vibrationally unresolved and broad detachment transitions consistent with significant differences in the molecular structures of the anion and neutral radical species. The experimental EAs and broad spectra are consistent with density functional theory calculations on these species. While the anion detachment transitions all involve an electron in a non-bonding orbital, the differences in structure between the neutral and anion are in part due to repulsion between the lone pair on the C-center on which the excess charge is localized and neighboring F atoms. The C6H5-xFx- (2 ≤ x ≤ 4) spectra show features at lower binding energy that appear to be due to constitutional isomers formed in the ion source.

Electronic Structure of Heteronuclear Cerium-Platinum Clusters.

Beyond the now well-known strong catalyst-support interactions reported for ceria-supported platinum catalysts, intermetallic Ce-Pt compounds exhibit fascinating properties such as heavy fermion behavior and magnetic instability. Small heterometallic Ce-Pt clusters, which can provide insights into the local features that govern bulk phenomena, have been less explored. Herein, the anion photoelectron spectra of three small mixed Ce-Pt clusters, Ce2OPt-, Ce2Pt-, and Ce3Pt-, are presented and interpreted with supporting density functional theory calculations. The calculations, which are readily reconciled with the experimental spectra, suggest the presence of numerous close-lying spin states, including states in which the Ce 4f electrons are ferromagnetically coupled or antiferromagnetically coupled. The Pt center is consistently in a nominal -2 charge state in all cluster neutrals and anions, giving the Ce-Pt bond ionic character. Ce-Pt bonds are stronger than Ce-Ce bonds, and the O atom in Ce2OPt- coordinates only with the Ce centers. The energy of the singly occupied Ce-local 4f orbitals relative to the Pt-local orbitals changes with cluster composition. Discussion of the results includes potential implications for Ce-rich intermetallic materials.

Probing Anion-Molecule Complexes of Atmospheric Relevance Using Anion Photoelectron Detachment Spectroscopy.

Bimolecular reaction and collision complexes that drive atmospheric chemistry and contribute to the absorption of solar radiation are fleeting and therefore inherently challenging to study experimentally. Furthermore, primary anions in the troposphere are short lived because of a complicated web of reactions and complex formation they undergo, making details of their early fate elusive. In this perspective, the experimental approach of photodetaching mass-selected anion-molecule complexes or complex anions, which prepares neutrals in various vibronic states, is surveyed. Specifically, the application of anion photoelectron spectroscopy along with photoelectron-photofragment coincidence spectroscopy toward the study of collision complexes, complex anions in which a partial covalent bond is formed, and radical bimolecular reaction complexes, with relevance in tropospheric chemistry, will be highlighted.

New Photoelectron-Valence Electron Interactions Evident in the Photoelectron Spectrum of Gd2O.

Evidence of strong photoelectron-valence electron (PEVE) interactions has been observed in the anion photoelectron (PE) spectra of several lanthanide suboxide clusters, which are exceptionally complex from an electronic structure standpoint and are strongly correlated systems. The PE spectrum of Gd2O-, which should have relatively simple electronic structure because of its half-filled 4f subshell, exhibits numerous electronic transitions. The electron affinity determined from the spectrum is 0.26 eV. The intensities of transitions to excited states increase relative to the lower-energy states with lower photon energy, which is consistent with shakeup transitions driven by time-dependent electron-neutral interactions. A group of intense spectral features that lie between electron binding energies of 0.7 and 2.3 eV are assigned to transitions involving detachment of an electron from outer-valence σu and σg orbitals that have large Gd 6s contributions. The spectra show parallel transition manifolds in general, which is consistent with detachment from these orbitals. However, several distinct perpendicular transitions are observed adjacent to several of the vertical transitions. A possible explanation invoking interaction between the ejected electron and the high-spin neutral is proposed. Specifically, the angular momentum of electrons ejected from σu or σg orbitals, which is l = 1, can switch to l = 0, 2 with an associated change in the Ms of the remnant neutral, which is spin-orbit coupling between a free electron and the spin of a neutral.

Identification of Isoprene Oxidation Reaction Products via Anion Photoelectron Spectroscopy.

We present a study on the oxidation of isoprene under several different conditions that may model both atmospheric and combustion chemistry. Anions, formed by passing isoprene/oxidant gas mixtures through a pulsed discharge generating a range of species, are separated via mass spectrometry and characterized by anion photoelectron (PE) spectroscopy supported by computations. Specifically, a UV-irradiated isoprene/O2 mixture, which additionally produces O3, and an isoprene/O2/H2 mixture, which generates •OH when passed through the discharge, were sampled. The mass spectra of ions generated under both conditions show the production of intact molecular ions, ion-molecule complexes (e.g., O2-, O4-, and O2-·isoprene), and singly deprotonated species (e.g., deprotonated isoprene, C5H7-). In addition, both smaller and oxidized fragments are observed using both gas mixtures, though relative abundances differ. From the UV-irradiated isoprene/O2 gas mixture, additional intact molecular products of reactions initiated by ozonolysis of isoprene, methylglyoxal, and dimethylglyoxal were observed. Fragmentation and oxidation of isoprene observed in both gas mixtures included species with m/z 39, 53, 67, 69, and 83 that we attribute to a series of alkyl- and alkenoxide-based anions. The coexistence of intact molecules and complexes with fragments and reaction products demonstrates the versatility of this ion source as a simple and efficient anion formation method for studying species that may be relevant in atmospheric and combustion chemistry.

Autodetachment over Broad Photon Energy Ranges in the Anion Photoelectron Spectra of [O2-M]- (M = Glyoxal, Methylglyoxal, or Biacetyl) Complex Anions.

Complexes of anion-neutral pairs are prevalent in chemical and physical processes in the interstellar medium, the atmosphere, and biological systems, among others. However, bimolecular anionic species that cannot be described as simple ion-molecule complexes due to their competitive electron affinities have received less attention. In this study, the [O2-M]- (M = glyoxal, methylglyoxal, or biacetyl) anion photoelectron spectra obtained with several different photon energies are reported and interpreted in the context of ab initio calculations. The spectra do not resemble the photoelectron spectra of M- or O2- "solvated" by a neutral partner. Rather, all spectra are dominated by near-threshold autodetachment from what are likely transient dipole bound states of the cis conformers of the complex anions. Very low Franck-Condon overlap between the neutral M·O2 van der Waals clusters and the partial covalently bound complex anions results in low-intensity, broad direct detachment observed in the spectra. The [O2-glyoxal]- spectra measured with 2.88 and 3.495 eV photon energies additionally exhibit features at ∼0.5 eV electron kinetic energy, which is more difficult to explain, though there are numerous quasibound states of the anion that may be involved. Overall, these features point to the inadequacy of describing the complex anions as simple ion-molecule complexes.

More than little fragments of matter: Electronic and molecular structures of clusters.

Small clusters have captured the imaginations of experimentalists and theorists alike for decades. In addition to providing insight into the evolution of properties between the atomic or molecular limits and the bulk, small clusters have revealed a myriad of fascinating properties that make them interesting in their own right. This perspective reviews how the application of anion photoelectron (PE) spectroscopy, typically coupled with supporting calculations, is particularly well-suited to probing the molecular and electronic structure of small clusters. Clusters provide a powerful platform for the study of the properties of local phenomena (e.g., dopants or defect sites in heterogeneous catalysts), the evolution of the band structure and the transition from semiconductor to metallic behavior in metal clusters, control of electronic structures of clusters through electron donating or withdrawing ligands, and the control of magnetic properties by interactions between the photoelectron and remnant neutral states, among other important topics of fundamental interest. This perspective revisits historical, groundbreaking anion PE spectroscopic finding and details more recent advances and insight gleaned from the PE spectra of small covalently or ionically bound clusters. The properties of the broad range of systems studied are uniquely small-cluster like in that incremental size differences are associated with striking changes in stability, electronic structures, and symmetry, but they can also be readily related to larger or bulk species in a broader range of materials and applications.

Lanthanide Oxides: From Diatomics to High-Spin, Strongly Correlated Homo- and Heterometallic Clusters.

Small lanthanide (Ln) oxide clusters present both experimental and theoretical challenges because of their partially filled, core-like 4f n orbitals, a feature that results in a plethora of close-lying and fundamentally similar electronic states. These clusters provide a bottom-up approach toward understanding the electronic structure of defective or doped bulk material but also can offer a challenge to the theorists to find a method robust enough to capture electronic structure patterns that emerge from within the 4f n (0 < n < 14) series. In this Feature Article, we explore the electronic structures of small lanthanide oxide clusters that deviate from bulk stoichiometry using anion photoelectron spectroscopy and supporting density functional theory calculations. We will describe the evolution of electronic structure with oxidation and how LnxOy- cluster reactivities can be correlated with specific Ln-local orbital occupancies. These strongly correlated systems offer additional insights into how interactions between electrons and electronically complex neutrals can lead to detachment transitions that lie outside of the sudden one-electron detachment approximation generally assumed in anion photoelectron spectroscopy. With a better understanding of how we can control nominally forbidden transitions to sample an array of spin states, we suggest that more in-depth studies on the magnetic states of these systems can be explored. Extending these studies to other Ln-based materials with hidden magnetic phases, along with sequentially ligated single molecule magnets, could advance current understanding of these systems.

Photoelectron Spectra of Gd2O2- and Nonmonotonic Photon-Energy-Dependent Variations in Populations of Close-Lying Neutral States.

Photoelectron spectra of Gd2O2- obtained with photon energies ranging from 2.033 to 3.495 eV exhibit numerous close-lying neutral states with photon-energy-dependent relative intensities. Transitions to these states, which fall within the electron binding energy window of 0.9 and 1.6 eV, are attributed to one- or two-electron transitions to the ground and low-lying excited neutral states. An additional, similar manifold of electronic states is observed in an electron binding energy window of 2.1-2.8 eV, which cannot be assigned to any simple one-electron transitions. This study expands on previous work on the Sm2O- triatomic, which has a more complex electronic structure because of the 4f6 subshell occupancy of each Sm center. Because of the simpler electronic structure from the half-filled 4f7 subshell occupancy in Gd2O2 and Gd2O2-, the numerous close-lying transitions observed in the spectra are better resolved, allowing a more detailed view of the changes in relative intensities of individual transitions with photon energy. With supporting calculations on numerous possible close-lying electronic states, we suggest a potential description of the strong photoelectron-valence electron interactions that may result in the photon-energy-dependent changes in the observed spectra.

Using anion photoelectron spectroscopy of cluster models to gain insights into mechanisms of catalyst-mediated H2 production from water.

Metal oxide cluster models of catalyst materials offer a powerful platform for probing the molecular-scale features and interactions that govern catalysis. This perspective gives an overview of studies implementing the combination of anion photoelectron (PE) spectroscopy and density functional theory calculations toward exploring cluster models of metal oxides and metal-oxide supported Pt that catalytically drive the hydrogen evolution reaction (HER) or the water-gas shift reaction. The utility in the combination of these experimental and computational techniques lies in our ability to unambiguously determine electronic and molecular structures, which can then connect to results of reactivity studies. In particular, we focus on the activity of oxygen vacancies modeled by suboxide clusters, the critical mechanistic step of forming proximal metal hydride and hydroxide groups as a prerequisite for H2 production, and the structural features that lead to trapped dihydroxide groups. The pronounced asymmetric oxidation found in heterometallic group 6 oxides and near-neighbor group 5/group 6 results in higher activity toward water, while group 7/group 6 oxides form very specific stoichiometries that suggest facile regeneration. Studies on the trans-periodic combination of cerium oxide and platinum as a model for ceria supported Pt atoms and nanoparticles reveal striking negative charge accumulation by Pt, which, combined with the ionic conductivity of ceria, suggests a mechanism for the exceptionally high activity of this system towards the water-gas shift reaction.

Temporary anion states of fluorine substituted benzenes probed by charge transfer in O2 -·C6H6-xFx (x = 0-5) ion-molecule complexes.

The broadband photoelectron source realized by detaching O2 -·X (X = neutral unsaturated molecule) complexes offers a unique opportunity to probe temporary anion states of the unsaturated species. Detachment of the ion molecule complex typically accesses a dissociative portion of the neutral potential, creating a continuum electron source that can undergo scattering with X. We present the application of this new approach to electron-neutral scattering toward a study of the series of fluorinated benzenes via photoelectron spectroscopy of O2 -·C6H6-xFx (x = 0-6) measured with several photon energies. We compare these spectra to the reference O2 -·hexane spectrum and observe evidence of temporary anion states of C6H6-xFx for species with x = 0-5 in the form of enhanced signal intensity at electron kinetic energies coinciding with the energies of the temporary anions. Furthermore, we observe autodetachment features in the x = 3, 5 spectra. Results of calculations on the isolated symmetric isomer of C6H3F3 suggest that the molecule cannot support a weakly-bound non-valence state that could be associated with the observed autodetachment. However, C6HF5 - is predicted to support a valence bound state, which, if produced by charge transfer from O2 - with sufficient vibrational energy, may undergo autodetachment. Finally, the [O2·C6F6]- spectrum is unique insofar as the spectrum is substantially higher in binding energy and qualitatively different from the x = 0-5 spectra. This result suggests much stronger interactions and charge delocalization between O2 - and C6F6.

The striking influence of oxophilicity differences in heterometallic Mo-Mn oxide cluster reactions with water.

Mixed-metal oxides have proven to be effective catalysts for the hydrogen evolution reaction, often outperforming either of the binary metal oxides. The reactivity of MnxMoOy - (x = 1, 2; y = 3, 4) clusters toward H2O was investigated via time-of-flight mass spectrometry with clear evidence of cluster oxidation and corresponding H2 production, specifically for MnxMoO3 - (x = 1, 2) clusters. Unlike previously studied MoxOy - clusters, which assumed a broad distribution of stoichiometries (typically x ≤ y ≤ 3x), both MnMoOy - and Mn2MoOy - preferentially formed y = 3 and 4 compositions in significant quantities under our source conditions. The electronic and molecular structures of the MnxMoOy (x = 1, 2; y = 3, 4) anion and neutral clusters were probed with anion photoelectron spectroscopy and analyzed with supporting density functional theory calculations. Our studies suggest that both metal centers are involved in initial cluster-water complex formation, while Mo is the center that undergoes oxidation; hence, reactivity terminates when Mo is saturated in its highest oxidation state of +6. Across these four clusters, Mn remains relatively reduced and is stable in a high-spin electronic configuration. The preferential reactivity of water molecules toward the Mo center rather than Mn is rationalized by the much lower relative oxophilicity of Mn.

Emerging Nonvalence Anion States of [Isoprene-H·]·H2O Accessed via Detachment of OH-·Isoprene.

The anion photoelectron imaging spectra of an ion with m/z 85, generated under ion source conditions that optimize •OH production in a coexpansion with isoprene, are presented and analyzed with supporting calculations. A spectroscopic feature observed at a vertical electron detachment energy of 2.45 eV, which dominates the photoelectron spectrum measured at 3.495 eV photon energy, is consistent with the OH-·isoprene ion-molecule complex, while additional signal observed at lower electron binding energy can be attributed to other constitutional isomers. However, spectra measured over a 2.2-2.6 eV photon energy range, i.e., from near threshold of the predominant OH-·isoprene detachment feature through the vertical detachment energy, exhibit sharp features with common electron kinetic energies, suggesting autodetachment from a temporary anion prepared by photoexcitation. The photon energy independence of the electron kinetic energy of these features along with the low dipole moment predicted for the neutral •OH·isoprene van der Waals complex, suggest a complex photon-driven process. We present calculations supporting a hypothesis that near-threshold production of the •OH···isoprene reactive complex results in hydrogen abstraction of the isoprene molecule. The newly formed activated complex anion supports a dipole bound state that temporarily traps the near zero-kinetic energy electron and then autodetaches, encoding the low-frequency modes of the dehydrogenated neutral isoprene radical in the electron kinetic energies.

Exceptionally Complex Electronic Structures of Lanthanide Oxides and Small Molecules.

Lanthanide (Ln) oxide clusters and molecular systems provide a bottom-up look at the electronic structures of the bulk materials because of close parallels in the patterns of Ln 4fN subshell occupancy between the molecular and bulk Ln2O3 size limits. At the same time, these clusters and molecules offer a challenge to the theory community to find appropriate and robust treatments for the 4fN patterns across the Ln series. Anion photoelectron (PE) spectroscopy provides a powerful experimental tool for studying these systems, mapping the energies of the ground and low-lying excited states of the neutral relative to the initial anion state, providing spectroscopic patterns that reflect the Ln 4fN occupancy. In this Account, we review our anion PE spectroscopic and computational studies on a range of small lanthanide molecules and cluster species. The PE spectra of LnO- (Ln = Ce, Pr, Sm, Eu) diatomic molecules show spectroscopic signatures associated with detachment of an electron from what can be described as a diffuse Ln 6s-like orbital. While the spectra of all four diatomics share this common transition, the fine structure in the transition becomes more complex with increasing 4f occupancy. This effect reflects increased coupling between the electrons occupying the corelike 4f and diffuse 6s orbitals with increasing N. Understanding the PE spectra of these diatomics sets the stage for interpreting the spectra of polyatomic molecular and cluster species. In general, the results confirm that the partial 4fN subshell occupancy is largely preserved between molecular and bulk oxides and borides. However, they also suggest that surfaces and edges of bulk materials may support a low-energy, diffuse Ln 6s band, in contrast to bulk interiors, in which the 6s band is destabilized relative to the 5d band. We also identify cases in which the molecular Ln centers have 4fN+1 occupancy rather than bulklike 4fN, which results in weaker Ln-O bonding. Specifically, Sm centers in mixed Ce-Sm oxides or in SmxOy- (y ≤ x) clusters have this higher 4fN+1 occupancy. The PE spectra of these particular species exhibit a striking increase in the relative intensities of excited-state transitions with decreasing photon energy (resulting in lower photoelectron kinetic energy). This is opposite of what is expected on the basis of the threshold laws that govern photodetachment. We relate this phenomenon to strong electron-neutral interactions unique to these complex electronic structures. The time scale of the interaction, which shakes up the electronic configuration of the neutral, increases with decreasing electron momentum. From a computational standpoint, we point out that special care must be taken when considering Ln cluster and molecular systems toward the center of the Ln series (e.g., Sm, Eu), where treatment of electrons explicitly or using an effective core potential can yield conflicting results on competing subshell occupancies. However, despite the complex electronic structures associated with partially filled 4fN subshells, we demonstrate that inexpensive and tractable calculations yield useful qualitative insight into the general electronic structural features.

Mo Insertion into the H2 Bond in MoxSy- + H2 Reactions.

A combined experimental and computational study of H2 reactions with small 98MoxSy- clusters ranging from subsulfide (x ∼ y) to hypersulfide (y > 2x) is presented. Results suggest that the subsulfides react with H2 primarily by insertion of a more reduced Mo center into the H-H bond, forming a dihydride product. We find that this reaction occurs up to Mo oxidation states of +4. For the subsulfides containing a second metal in a sufficiently low oxidation state, a second insertion of H2 occurs, leading to a tetrahydride product. The reaction mechanisms of the sulfides are found to be very similar, albeit slightly higher energetically to those of the analogous oxosulfides that are also observed at low abundances in the experiments. In addition, the experimental results show an overall reduction of hypersulfides in the presence of H2, suggesting loss of H2S neutral molecules.

Electronic and Molecular Structures of the CeB6 Monomer.

The electronic and molecular structure of the CeB6 molecular unit has been probed by anion PE spectroscopy and DFT calculations to gain insight into structural and electronic relaxation on edge and corner sites of this ionic material. While boron in bulk lanthanide hexaboride materials assumes octahedral B63- units, the monomer assumes a less compact structure to delocalize the charge. Two competitive molecular structures were identified for the anion and neutral species, which include a boat-like structure and a planar or near-planar teardrop structure. Ce adopts different orbital occupancies in the two isomers; the boat-like structure has a 4f superconfiguration while the teardrop favors a 4f 6s occupancy. The B6 ligand in these structures carries a charge of -4 and -3, respectively. The teardrop structure, which was calculated to be isoenergetic with the boat structure, was most consistent with the experimental spectrum. B6-local orbitals crowd the energy window between the Ce 4f and 6s (HOMO) orbitals. A low-lying transition from the B-based orbitals is observed slightly less than 1 eV above the ground state. The results suggest that edge and corner conductivity involves stabilized, highly diffuse 6s orbitals or bands rather than the bulk-favored 5d band. High-spin and open-shell low-spin states were calculated to be very close in energy for both the anion and neutral, a characteristic that reflects how decoupled the 4f electron is from the B6 2p- and Ce 6s-based molecular orbitals.

Probing alkenoxy radical electronic structure using anion PEI spectroscopy.

Photoelectron imaging spectra of three alkenoxide radical anions (3-buten-1-oxide, 3-buten-2-oxide, and 2-propenoxide) are presented and analyzed with supporting results of density functional theory calculations. In all spectra, intense detachment features are observed at approximately 2 eV electron binding energy, which is similar to the electron affinities of saturated neutral alkoxy radicals [Ramond et al., J. Chem. Phys. 112, 1158 (2000)]. Photoelectron angular distributions suggest the presence of several overlapping transitions which are assigned to the X̃ and à states of multiple energetically competitive conformers. The term energy of the à state of the 2-propenoxy radical, 0.17 eV, is higher than that of 3-buten-2-oxy (0.13 eV) and 3-buten-1-oxy (0.05 eV) radicals. Comparing the butenoxy radicals, we infer that stronger interactions between the non-bonding O 2p orbitals and the π bond increase the splitting between the ground and the first excited state in the 3-buten-2-oxy radical relative to the 3-buten-1-oxy radical.