Probing the dynamics and bottleneck of the key atmospheric SO2 oxidation reaction by the hydroxyl radical.

SO2 (Sulfur dioxide) is the major precursor to the production of sulfuric acid (H2SO4), contributing to acid rain and atmospheric aerosols. Sulfuric acid formed from SO2 generates light-reflecting sulfate aerosol particles in the atmosphere. This property has prompted recent geoengineering proposals to inject sulfuric acid or its precursors into the Earth's atmosphere to increase the planetary albedo to counteract global warming. SO2 oxidation in the atmosphere by the hydroxyl radical HO to form HOSO2 is a key rate-limiting step in the mechanism for forming acid rain. However, the dynamics of the HO + SO2 → HOSO2 reaction and its slow rate in the atmosphere are poorly understood to date. Herein, we use photoelectron spectroscopy of cryogenically cooled HOSO2- anion to access the neutral HOSO2 radical near the transition state of the HO + SO2 reaction. Spectroscopic and dynamic calculations are conducted on the first ab initio-based full-dimensional potential energy surface to interpret the photoelectron spectra of HOSO2- and to probe the dynamics of the HO + SO2 reaction. In addition to the finding of a unique pre-reaction complex (HO⋯SO2) directly connected to the transition state, dynamic calculations reveal that the accessible phase space for the HO + SO2 → HOSO2 reaction is extremely narrow, forming a key reaction bottleneck and slowing the reaction rate in the atmosphere, despite the low reaction barrier. This study underlines the importance of understanding the full multidimensional potential energy surface to elucidate the dynamics of complex bimolecular reactions involving polyatomic reactants.

Searching for stable copper borozene complexes in CuB7- and CuB8.

Copper has been shown to be an important substrate for the growth of borophenes. Copper-boron binary clusters are ideal platforms to study the interactions between copper and boron, which may provide insight about the underlying growth mechanisms of borophene on copper substrates. Here we report a joint photoelectron spectroscopy and theoretical study on two copper-doped boron clusters, CuB7- and CuB8-. Well resolved photoelectron spectra are obtained for the two clusters at different wavelengths and are used to understand the structures and bonding properties of the two CuBn- clusters. We find that CuB8- is a highly stable borozene complex, which possesses a half-sandwich structure with a Cu+ species interacting with the doubly aromatic η8-B82- borozene. The CuB7- cluster is found to consist of a terminal copper atom bonded to a double-chain B7 motif, but it has a low-lying isomer composed of a half-sandwich structure with a Cu+ species interacting with an open-shell η7-B72- borozene. Both ionic and covalent interactions are found to be possible in the binary Cu-B clusters, resulting in different structures.

Investigation of Pb-B Bonding in PbB2(BO)n- (n = 0-2): Transformation from Aromatic PbB2- to Pb[B2(BO)2]-/0 Complexes with BB Triple Bonds.

Boron has been found to be able to form multiple bonds with lead. To probe Pb-B bonding, here we report an investigation of three Pb-doped boron clusters, PbB2-, PbB3O-, and PbB4O2-, which are produced by a laser ablation cluster source and characterized by photoelectron spectroscopy and ab initio calculations. The most stable structures of PbB2-, PbB3O-, and PbB4O2- are found to follow the formula, [PbB2(BO)n]- (n = 0-2), with zero, one, and two boronyl ligands coordinated to a triangular and aromatic PbB2 core, respectively. The PbB2- cluster contains a BB double bond and two Pb-B single bonds. The coordination of BO is observed to weaken Pb-B bonding but strengthen the BB bond in [PbB2(BO)n]- (n = 1, 2). The anionic [PbB2(BO)2]- and its corresponding neutral closed-shell [PbB2(BO)2] contain a BB triple bond. A low-lying Y-shaped isomer is also observed for PbB4O2-, consisting of a central sp2 hybridized B atom bonded to two boronyl ligands and a PbB unit.

High-Resolution Photoelectron Imaging of Cryogenically Cooled BiB2- and BiB3- Bismuth-Boron Clusters.

We report a high-resolution photoelectron imaging study of cryogenically cooled BiB2- and BiB3- clusters. Vibrational features are completely resolved for the ground-state detachment transitions, providing critical information about the structures of the anionic clusters and their corresponding neutrals. The electron affinities of BiB2 and BiB3 are accurately measured to be 2.174(1) and 2.121(1) eV, respectively. The B-B and Bi-B stretching frequencies are measured to be 1262 and 476 cm-1, respectively, in the ground state of BiB2. Three vibrational frequencies are measured for the ground state of BiB3: 1194 cm-1 (B-B stretching), 782 cm-1 (B-B stretching), and 339 cm-1 (Bi-B stretching). Both BiB2- and BiB3- and their neutral ground states are found to have planar C2v structures in which the Bi atom bridges two B atoms. BiB2- is found to have a triplet spin state (3B2), consistent with its complicated photoelectron spectra, whereas BiB3- is a doublet (2B1) and neutral BiB3 is closed shell (1A1). Both BiB2 and BiB3 consist of peripheral localized Bi-B and B-B σ bonds and delocalized π and σ bonds.

Electronic Control of the Position of the Pb Atom on the Surface of B8 Borozene in the PbB8 Cluster.

Spontaneous symmetry-breaking is common in chemical and physical systems. Here, we show that by adding an electron to the C7v PbB8 cluster, which consists of a planar B8 disk with the Pb atom situated along the C7 axis, the Pb atom spontaneously moves to the off-axis position in the PbB8- anion. Photoelectron spectroscopy of PbB8- reveals a broad ground-state transition and a large energy gap, suggesting a highly stable closed-shell PbB8 borozene complex and a significant geometry change upon electron detachment. Quantum chemistry calculations indicate that the lowest unoccupied molecular orbital of the C7v PbB8 cluster is a degenerate π orbital mainly consisting of the Pb 6px and 6py atomic orbitals. Occupation of one of the 6p orbitals spontaneously break the C7v symmetry in the anion due to the Jahn-Teller effect. The large amplitude of the position change of Pb in PbB8- relative to PbB8 is surprising owing to bonding interactions between the Pb 6p orbital with the π orbital of the B8 borozene.

Observation of bound valence excited electronic states of deprotonated 2-hydroxytriphenylene using photoelectron, photodetachment, and resonant two-photon detachment spectroscopy of cryogenically cooled anions.

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh-), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh- anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh- anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh-, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3 eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh- would be an interesting system for pump-probe experiments to unravel the dynamics of the excited states of this complex PAH anion.

Formation of Supernarrow Borophene Nanoribbons.

Borophenes have sparked considerable interest owing to their fascinating physical characteristics and diverse polymorphism. However, borophene nanoribbons (BNRs) with widths less than 2 nm have not been achieved. Herein, we report the experimental realization of supernarrow BNRs. Combining scanning tunneling microscopy imaging with density functional theory modeling and ab initio molecular dynamics simulations, we demonstrate that, under the applied growth conditions, boron atoms can penetrate the outermost layer of Au(111) and form BNRs composed of a pair of zigzag (2,2) boron rows. The BNRs have a width self-contained to ∼1 nm and dipoles at the edges to keep them separated. They are embedded in the outermost Au layer and shielded on top by the evacuated Au atoms, free of the need for post-passivation. Scanning tunneling spectroscopy reveals distinct edge states, primarily attributed to the localized spin at the BNRs' zigzag edges. This work adds a new member to the boron material family and introduces a new physical feature to borophenes.

Observation of a Polarization-Assisted Dipole-Bound State.

The critical dipole moment to bind an electron was empirically determined to be 2.5 debye, even though smaller values were predicted theoretically. Herein, we report the first observation of a polarization-assisted dipole-bound state (DBS) for a molecule with a dipole moment below 2.5 debye. Photoelectron and photodetachment spectroscopies are conducted for cryogenically cooled indolide anions, where the neutral indolyl radical has a dipole moment of 2.4 debye. The photodetachment experiment reveals a DBS only 6 cm-1 below the detachment threshold along with sharp vibrational Feshbach resonances. Rotational profiles are observed for all of the Feshbach resonances, which are found to have surprisingly narrow linewidths and long autodetachment lifetimes attributed to weak coupling between vibrational motions and the nearly free dipole-bound electron. Calculations suggest that the observed DBS has π-symmetry stabilized by the strong anisotropic polarizability of indolyl.

Role of Polarization Interactions in the Formation of Dipole-Bound States.

Even though there is a critical dipole moment required to support a dipole-bound state (DBS), how molecular polarizability may influence the formation of DBSs is not well understood. Pyrrolide, indolide, and carbazolide provide an ideal set of anions to systematically examine the role of polarization interactions in the formation of DBSs. Here, we report an investigation of carbazolide using cryogenic photodetachment spectroscopy and high-resolution photoelectron spectroscopy (PES). A polarization-assisted DBS is observed at 20 cm-1 below the detachment threshold for carbazolide, even though the carbazolyl neutral core has a dipole moment (2.2 D) smaller than the empirical critical value (2.5 D) to support a dipole-bound state. Photodetachment spectroscopy reveals nine vibrational Feshbach resonances of the DBS, as well as three intense and broad shape resonances. The electron affinity of carbazolyl is measured accurately to be 2.5653 ± 0.0004 eV (20,691 ± 3 cm-1). The combination of photodetachment spectroscopy and resonant PES allows fundamental frequencies for 14 vibrational modes of carbazolyl to be measured. The three shape resonances are due to above-threshold excitation to the three low-lying electronic states (S1-S3) of carbazolide. Resonant PES of the shape resonances is dominated by autodetachment processes. Ultrafast relaxation from the S2 and S3 states to S1 is observed, resulting in constant kinetic energy features in the resonant PES. The current study provides decisive information about the role that polarization plays in the formation of DBSs, as well as rich spectroscopic information about the carbazolide anion and the carbazolyl radical.

Probing the Nature of the Transition-Metal-Boron Bonds and Novel Aromaticity in Small Metal-Doped Boron Clusters Using Photoelectron Spectroscopy.

Photoelectron spectroscopy combined with quantum chemistry has been a powerful approach to elucidate the structures and bonding of size-selected boron clusters (Bn-), revealing a prevalent planar world that laid the foundation for borophenes. Investigations of metal-doped boron clusters not only lead to novel structures but also provide important information about the metal-boron bonds that are critical to understanding the properties of boride materials. The current review focuses on recent advances in transition-metal-doped boron clusters, including the discoveries of metal-boron multiple bonds and metal-doped novel aromatic boron clusters. The study of the RhB- and RhB2O- clusters led to the discovery of the first quadruple bond between boron and a transition-metal atom, whereas a metal-boron triplebond was found in ReB2O- and IrB2O-. The ReB4- cluster was shown to be the first metallaborocycle with Möbius aromaticity, and the planar ReB6- cluster was found to exhibit aromaticity analogous to metallabenzenes.

Photoelectron Spectroscopy and Theoretical Study of Di-Copper-Boron Clusters: Cu2B3- and Cu2B4.

Copper has been found to be able to mediate the formation of bilayer borophenes. Copper-boron binary clusters are ideal model systems to probe the copper-boron interactions, which are essential to understand the growth mechanisms of borophenes on copper substrates. Here, we report a joint photoelectron spectroscopy and theoretical study on two di-copper-doped boron clusters: Cu2B3- and Cu2B4-. Well-resolved photoelectron spectra are obtained, revealing the presence of a low-lying isomer in both cases. Theoretical calculations show that the global minimum of Cu2B3- (C2v, 1A1) contains a doubly aromatic B3- unit weakly interacting with a Cu2 dimer, while the low-lying isomer (C2v, 1A1) consists of a B3 triangle with the two Cu atoms covalently bonded to two B atoms at two vertexes. The global minimum of Cu2B4- (D2h, 2Ag) is found to consist of a rhombus B4 unit covalently bonded to the two Cu atoms at two opposite vertexes, whereas in the low-lying isomer (Cs, 2A'), one of the two Cu atoms is bonded to two B atoms.

On the electronic structure and spin-orbit coupling of BiB from photoelectron imaging of cryogenically-cooled BiB- anion.

We report a study on the electronic structure and chemical bonding of the BiB molecule using high-resolution photoelectron imaging of cryogenically cooled BiB- anion. By eliminating all the vibrational hot bands, we can resolve the complicated detachment transitions due to the open-shell nature of BiB and the strong spin-orbit coupling. The electron affinity of BiB is measured to be 2.010(1) eV. The ground state of BiB- is determined to be 2Π(3/2) with a σ2π3 valence electron configuration, while the ground state of BiB is found to be 3Σ-(0+) with a σ2π2 electron configuration. Eight low-lying spin-orbit excited states [3Σ-(1), 1Δ(2), 1Σ+(0+), 3Π(2), 3Π(1), 1Π(1)], including two forbidden transitions, [3Π(0-) and 3Π(0+)], are observed for BiB as a result of electron detachment from the σ and π orbitals of BiB-. The angular distribution information from the photoelectron imaging is found to be critical to distinguish detachment transitions from the σ or π orbital for the spectral assignment. This study provides a wealth of information about the low-lying electronic states and spin-orbit coupling of BiB, demonstrating the importance of cryogenic cooling for obtaining well-resolved photoelectron spectra for size-selected clusters produced from a laser vaporization cluster source.

Selective Semihydrogenation of Polarized Alkynes by a Gold Hydride Nanocluster.

The hydridic hydrogen in nanogold catalysts has long been postulated as an important intermediate in hydrogenation reactions, but it has not been directly observed. Here, we report the synthesis of a new undecagold cluster with a bidentate phosphine ligand. The chelating effects of the bidentate ligand result in a more symmetric Au11 core with two labile Cl- ligands that can exchange with BH4-, leading to a novel undecagold hydride cluster. The new hydride cluster is discovered to readily undergo hydroauration reaction with alkynes containing electron-withdrawing groups, forming key gold-alkenyl semihydrogenation intermediates, which can be efficiently and selectively converted to Z-alkenes under acidic conditions. All key reaction intermediates are isolated and characterized, providing atomic-level insights into the active sites and mechanisms of semihydrogenation reactions catalyzed by gold-based nanomaterials. The hydridic hydrogen in the undecagold cluster is found to be the key to prevent over hydrogenation of alkenes to alkanes. The current study provides fundamental insights into hydrogenation chemistry enabled by gold-based nanomaterials and may lead to the development of efficient catalysts for selective semihydrogenation or functionalization of alkynes.

Probing the Strong Nonadiabatic Interactions in the Triazolyl Radical Using Photodetachment Spectroscopy and Resonant Photoelectron Imaging of Cryogenically Cooled Anions.

Although the adiabatic potential energy surfaces defined by the Born-Oppenheimer approximation are the cornerstones for understanding the electronic structure and spectroscopy of molecular systems, nonadiabatic effects due to the coupling of electronic states by nuclear motions are common in complex molecular systems. The nonadiabatic effects were so strong in the 1,2,3-triazolyl radical (C2H2N3) that the photoelectron spectrum of the triazolide anion was rendered unassignable and could only be understood using nonadiabatic calculations, involving the four low-lying electronic states of triazolyl. Using photodetachment spectroscopy and resonant photoelectron imaging of cryogenically cooled anions, we are able to completely unravel the complex vibronic levels of the triazolyl radical. Photodetachment spectroscopy reveals a dipole-bound state for the triazolide anion at 172 cm-1 below the detachment threshold and 32 vibrational Feshbach resonances. Resonant photoelectron imaging is conducted by tuning the detachment laser to each of the Feshbach resonances. Combining the photodetachment spectrum and the resonant photoelectron spectra, we are able to assign all 28 vibronic peaks resolved for the triazolyl radical. Fundamental frequencies for 12 vibrational modes of the ground state of the triazolyl radical are measured experimentally. The current study provides unprecedented experimental vibronic information, which will be valuable to verify theoretical models to treat nonadiabatic effects involving multiple electronic states.

Probing the Electronic Structure and Bond Dissociation of SO3 and SO3- Using High-Resolution Cryogenic Photoelectron Imaging.

The SO3 molecule and its radical anion SO3- are important chemical species atmospherically. However, their thermodynamic properties and electronic structures are not well known experimentally. Using cryogenically cooled anions, we have obtained high-resolution photoelectron images of SO3- and determined accurately the electron affinity (EA) of SO3 and the bond dissociation energy of SO3- → SO2 + O- for the first time. Because of the large geometry changes from the C3v SO3- to the D3h SO3, there is a negligible Franck-Condon factor (FCF) for the 0-0 detachment transition, that defines the EA of SO3. By fitting the high-resolution photoelectron spectra with computed FCFs using structures from high-level ab initio calculations, we have determined the EA of SO3 to be 2.126(6) eV. By monitoring the appearance of the O- signal in the photoelectron images at different photon energies, we are able to measure directly the bond dissociation energy of SO3-(X2A1) → SO2(X1A1) + O-(2P) to be 4.259 ± 0.006 eV, which also allow us to derive the dissociation energy for the spin-forbidden SO3(X1A1') → SO2(X1A1) + O(3P) to be 3.594(6) eV. The excited states of SO3- are calculated using high-level ab initio calculations, which are valuable in aiding the interpretation of autodetachment processes observed at various photon energies. The current study provides valuable information about the fundamental molecular properties of SO3, as well as the radical anion SO3-, which is known in redox reactions involving SO32- and may also play a role in the chemistry of SO2 in the atmosphere.

A Heteroleptic Gold Hydride Nanocluster for Efficient and Selective Electrocatalytic Reduction of CO2 to CO.

It has been a long-standing challenge to create and identify the active sites of heterogeneous catalysts, because it is difficult to precisely control the interfacial chemistry at the molecular level. Here we report the synthesis and catalysis of a heteroleptic gold trihydride nanocluster, [Au22H3(dppe)3(PPh3)8]3+ [dppe = 1,2-bis(diphenylphosphino)ethane, PPh3 = triphenylphosphine]. The Au22H3 core consists of two Au11 units bonded via six uncoordinated Au sites. The three H atoms bridge the six uncoordinated Au atoms and are found to play a key role in catalyzing electrochemical reduction of CO2 to CO with a 92.7% Faradaic efficiency (FE) at -0.6 V (vs RHE) and high reaction activity (134 A/gAu mass activity). The CO current density and FECO remained nearly constant for the CO2 reduction reaction for more than 10 h, indicating remarkable stability of the Au22H3 catalyst. The Au22H3 catalytic performance is among the best Au-based catalysts reported thus far for electrochemical reduction of CO2. Density functional theory (DFT) calculations suggest that the hydride coordinated Au sites are the active centers, which facilitate the formation of the key *COOH intermediate.

Probing the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals using high-resolution photoelectron imaging of cryogenically cooled anions.

High-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled pyrrolide and imidazolide anions are used to probe the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals. The high-resolution data allow the ground state vibronic structures of the two radicals to be completely resolved, yielding accurate electron affinities of 2.1433 ± 0.0008 eV and 2.6046 ± 0.0006 eV for pyrrolyl and imidazolyl radicals, respectively. Fundamental frequencies for eight vibrational modes of pyrrolyl and ten vibrational modes of imidazolyl are measured, including several nonsymmetric Franck-Condon-forbidden modes. Two electronic excited states are also observed for the two radicals, displaying diffuse spectral features in both systems. The observations of nonsymmetric vibrational modes in the ground states and the diffuse excited state features provide strong evidence for vibronic couplings between the ground state and the two close-by excited states. The 2-pyrrolide isomer is also observed as a minor species from the electrospray ionization source and the electron affinity of 2-pyrrolyl is measured to be 1.6690 ± 0.0030 eV along with five vibrational frequencies. Even though the HOMOs of both pyrrolide and imidazolide anions are p orbitals, photodetachment spectroscopy reveals completely different threshold behaviors for the two anions: a d-wave-dominated spectrum for pyrrolide and an s-wave-dominated spectrum for imidazolide. The current study provides a wealth of electronic and spectroscopic information, which is ideal to compare with more accurate vibronic coupling calculations for these two important radicals, as well as interesting information about the photodetachment dynamics of the two anions.

Resonant two-photon photoelectron imaging and adiabatic detachment processes from bound vibrational levels of dipole-bound states.

Anions cannot have Rydberg states, but anions with polar neutral cores can support highly diffuse dipole-bound states (DBSs) as a class of interesting electronically excited states below the electron detachment threshold. The binding energies of DBSs are extremely small, ranging from a few to few hundred wavenumbers and generally cannot support bound vibrational levels below the detachment threshold. Thus, vibrational excitations in the DBS are usually above the electron detachment threshold and they have been used to conduct resonant photoelectron spectroscopy, which is dominated by state-specific autodetachment. Here we report an investigation of a cryogenically-cooled complex anion, the enantiopure (R)-(-)-1-(9-anthryl)-2,2,2-trifluoroethanolate (R-TFAE-). The neutral R-TFAE radical is relatively complex and highly polar with a non-planar structure (C1 symmetry). Photodetachment spectroscopy reveals a DBS 209 cm-1 below the detachment threshold of R-TFAE- and seven bound and eight above-threshold vibrational levels of the DBS. Resonant two-photon detachment (R2PD) via the bound vibrational levels of the DBS exhibits strictly adiabatic photodetachment behaviors by the second photon, in which the vibrational energies in the DBS are carried to the neutral final states, because of the parallel potential energy surfaces of the DBS and the corresponding neutral ground electronic state. Relaxation processes from the bound DBS levels to the ground and low-lying electronically excited states of R-TFAE- are also observed in the R2PD photoelectron spectra. The combination of photodetachment and resonant photoelectron spectroscopy yields frequencies for eight vibrational modes of the R-TFAE radical.

Dipole-Bound State, Photodetachment Spectroscopy, and Resonant Photoelectron Imaging of Cryogenically-Cooled 2-Cyanopyrrolide.

Valence-bound anions with polar neutral cores can have diffuse dipole-bound excited states just below the electron detachment threshold. Because of the similarity in geometry and vibrational frequencies between the dipole-bound states (DBSs) and the corresponding neutrals, DBSs have been exploited as intermediate states to conduct resonant photoelectron spectroscopy (PES), resulting in highly non-Franck-Condon photoelectron spectra via vibrational autodetachment and providing much richer vibrational information than conventional PES. Here, we report a photodetachment and high-resolution photoelectron imaging study of the 2-cyanopyrrolide anion, cooled in a cryogenic ion trap. The electron affinity of the 2-cyanopyrrolyl radical is measured to be 3.0981 ± 0.0006 eV (24 988 ± 5 cm-1). A DBS is observed for 2-cyanopyrrolide at 240 cm-1 below its detachment threshold using photodetachment spectroscopy. Twenty-three above-threshold vibrational resonances (Feshbach resonances) of the DBS are observed. Resonant PES is conducted at each Feshbach resonance, yielding a wealth of vibrational information about the 2-cyanopyrrolyl radical. Resonant two-photon PES confirms the s-like dipole-bound orbital and reveals a relatively long lifetime of the bound zero-point level of the DBS. Fundamental frequencies for 19 vibrational modes (out of a total of 24) are obtained for the cyanopyrrolyl radical, including six out-of-plane modes. The current work provides important spectroscopic information about 2-cyanopyrrolyl, which should be valuable for the study of this radical in combustion or astronomical environments.

Photoelectron imaging of cryogenically cooled BiO- and BiO2 - anions.

The advent of ion traps as cooling devices has revolutionized ion spectroscopy as it is now possible to efficiently cool ions vibrationally and rotationally to levels where truly high-resolution experiments are now feasible. Here, we report the first results of a new experimental apparatus that couples a cryogenic 3D Paul trap with a laser vaporization cluster source for high-resolution photoelectron imaging of cold cluster anions. We have demonstrated the ability of the new apparatus to efficiently cool BiO- and BiO2 - to minimize vibrational hot bands and allow high-resolution photoelectron images to be obtained. The electron affinities of BiO and BiO2 are measured accurately for the first time to be 1.492(1) and 3.281(1) eV, respectively. Vibrational frequencies for the ground states of BiO and BiO2, as well as those for the anions determined from temperature-dependent studies, are reported.