PE Spectra Research Articles

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.

A Comparative XPS, UV PES, NEXAFS, and DFT Study of the Electronic Structure of the Salen Ligand in the H2(Salen) Molecule and the [Ni(Salen)] Complex.

A comparative study of the electronic structure of the salen ligand in the H2(Salen) molecule and the [Ni(Salen)] complex was performed using the experimental methods of XPS, UV PES, and NEXAFS spectroscopy along with DFT calculations. Significant chemical shifts of +1.0 eV (carbon), +1.9 eV (nitrogen), and -0.4 eV (oxygen) were observed in the 1s PE spectra of the salen ligand atoms when passing from a molecule to a complex, unambiguously indicating a substantial redistribution of the valence electron density between these atoms. It is proposed that the electron density transfer to the O atoms in [Ni(Salen)] occurred not only from the Ni atom, but also from the N and C atoms. This process seemed to be realized through the delocalized conjugated π-system of the phenol C 2p electronic states of the ligand molecule. The DFT calculations (total and partial DOS) for the valence band H2(Salen) and [Ni(Salen)] described well the spectral shape of the UV PE spectra of both compounds and confirmed their experimental identification. An analysis of the N and O 1s NEXAFS spectra clearly indicated that the atomic structure of the ethylenediamine and phenol fragments was retained upon passing from the free salen ligand to the nickel complex.

Electron Affinities of Ligated Icosahedral M13 Superatoms Revisited by Gas-Phase Anion Photoelectron Spectroscopy.

The electron binding energies of the ligand-protected gold/silver-based cluster anions, [Au25(SR)18]-, [XAg24(SR')18]2- (X = Ag+, Au+, Pd0, or Pt0), and [PdAu24(C≡CR″)18]2- having icosahedral M13 superatomic cores, were reexamined by gas-phase photoelectron spectroscopy (PES) on a significantly intensified mass-selected ion beam. Laser fluence-dependent PE spectra and pump-probe PES revealed that the previous PE spectra were contaminated by PE signals due to the two-photon electron detachment via long-lived photoexcited states. Although the adiabatic electron affinities (AEAs) of the corresponding oxidized forms were found to be 1-2 eV larger than those previously reported, the effects of doping and ligation were not qualitatively affected. (1) The AEA of the Ag13 superatom (∼4 eV) was not appreciably affected by doping a Au atom at the center but was reduced by ∼2 eV by doping Pd or Pt, and (2) the AEA of PdAu12 protected by Au2(C≡CR″)3 units was much larger than that of PdAg12 protected by Ag2(SR')3 units.

The Valence Band Structure of the [Ni(Salen)] Complex: An Ultraviolet, Soft X-ray and Resonant Photoemission Spectroscopy Study

The valence band photoemission (VB PE) spectra of the [Ni(Salen)] molecular complex were measured by ultraviolet, soft X-ray and resonant photoemission (ResPE) using photons with energies ranging from 21.2 eV to 860 eV. It was found that the Ni 3d atomic orbitals’ (AOs) contributions are most significant for molecular orbitals (MOs), which are responsible for the low-energy PE band at a binding energy of 3.8 eV in the VB PE spectra. In turn, the PE bands in the binding energies range of 8–16 eV are due to the photoionization of the MOs of the [Ni(Salen)] complex with dominant contributions from C 2p AOs. A detailed consideration was made for the ResPE spectra obtained using photons with absorption resonance energies in the Ni 2p3/2, N 1s, and O 1s Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra. A strong increase in the intensity of the PE band ab was found when using photons with an energy 854.4 eV in the Ni 2p3/2 NEXAFS spectrum. This finding is due to the high probability of the participator-Auger decay of the Ni 2p3/2−13d9 excitation and confirms the relationship between the PE band ab with the Ni 3d-derived MOs.

Beyond Born-Oppenheimer based diabatic surfaces of 1,3,5-C6H3F3+ to generate the photoelectron spectra using time-dependent discrete variable representation approach.

In this article, Beyond Born-Oppenheimer (BBO) treatment is implemented to construct diabatic potential energy surfaces (PESs) of 1,3,5-C6H3F3+ over a series [eighteen (18)] of two-dimensional (2D) nuclear planes constituted with eleven normal modes (Q2, Q9x, Q9y, Q13x, Q13y, Q18x, Q18y, Q10x, Q10y, Q12x and Q12y) to include all possible nonadiabatic interactions among six coupled electronic states (X̃2E'', , B̃2E' and ). We had formulated explicit expressions of adiabatic to diabatic transformation (ADT) equations [S. Mukherjee, J. Dutta, B. Mukherjee, S. Sardar and S. Adhikari, J. Chem. Phys., 2019, 150, 064308] for the same system forming six state sub-Hilbert space and at present, these ADT equations are solved by incorporating MRCI level ab initio adiabatic PESs and CP-MCSCF calculated nonadiabatic coupling terms (NACTs) to derive diabatic PESs and couplings. Such single-valued, smooth, symmetric and continuous diabatic surface matrices are utilized to carry out multi-state multi-mode nuclear dynamics with the help of time-dependent discrete variable representation (TDDVR) methodology to compute the photoelectron (PE) spectra of 1,3,5-C6H3F3. Our theoretically calculated spectra for X̃2E'', and states using BBO treatment and TDDVR dynamics show peak by peak correspondence with the experimental results as well as better than the findings of the multi-configuration time-dependent Hartree (MCTDH) method.

Theoretical characterization of the endohedral metalloborospherenes M@B36 (M = Ti, Zr, Hf, Ce, Th, Pa+, U2+, Np3+, and Pu4+)

A series of endohedral metalloborospherenes M@B36 (M = Ti, Zr, Hf, Ce, Th, Pa+, U2+, Np3+, and Pu4+) were investigated through density functional theory. This series of metal atom/ion encapsulated B36 cage meet the 32-electron principle as evidenced with the strong participations of An 7s, 7p, 6d and 5f orbitals in the orbital hybridizations. High stabilities of the endohedral metalloborospherenes have been rationalized in terms of larger HOMO-LUMO gap and negative values of reaction enthalpy and free energy. Electron density topological analyses were performed with QTAIM and AdNDP methods to understand the binding nature of these complexes. Furthermore, IR and PES spectra were simulated to aid future experimental characterization of studied species.

Electron Binding in a Superatom with a Repulsive Coulomb Barrier: The Case of [Ag44(SC6H3F2)30]4- in the Gas Phase.

The electron binding mechanism in [Ag44(SC6H3F2)30]4- (SC6H3F2 = 3,4-difluorobenzenethiolate) tetra-anion was studied by photoelectron spectroscopy (PES), collision-induced dissociation mass spectrometry (CID-MS), and density functional theory (DFT) computations. PES showed that [Ag44(SC6H3F2)30]4- is energetically metastable with respect to electron autodetachment {[Ag44(SC6H3F2)30]3- + e-} and features a repulsive Coulomb barrier (RCB) with a height of 2.7 eV. However, CID-MS revealed that [Ag44(SC6H3F2)30]4- does not release an electron upon collisional excitation but undergoes dissociation. DFT computations performed on the known structure of [Ag44(SC6H3F2)30]4- confirmed the negative adiabatic electron affinity of [Ag44(SC6H3F2)30]3- and interpreted the experimental PE spectrum by taking into account tunneling electron photodetachment through the RCB.

First-principles study of AuSn (2 ≤ n ≤ 7) clusters: structural, electronic, magnetic, spectral properties, and adsorption properties with O2 and H2O

Based on the density functional theory (DFT) method, the geometrical structures, relative stability, electronic, and spectral properties of AuSn (2 ≤ n ≤ 7) clusters are systematically studied, whose sizes are largely in the range of 0.3–0.5 nm. AuS4 and AuS3 show the highest and lowest energy gaps and hence the highest chemical stability and chemical activity, respectively. The total magnetic moment is 3.0 and 1 (or 0) μB for AuS4 and other clusters, respectively, which largely (about 99.9%) arise from the local magnetic moment of S atoms. The average polarization tensor for single atom ( ) generally increases with increasing the number of S atoms, with the maximum 91.72 a.u. for AuS7, corresponding to the most significant delocalization effect. AuS4 cluster exhibits the highest polarizability anisotropic invariant Δα (≈ 350.56 a.u.) and the lowest total dipole moment (≈ 0.06 D) among all systems, corresponding to the strongest anisotropic response to external electric field and the weakest polarization, respectively. The IR, Raman, UV-Vis, and PES spectra are simulated for AuSn (2 ≤ n ≤ 7) clusters with the structures of the lowest isomers. The O–O and O–H bond lengths, adsorption energies, vibration frequencies, and density of states are also calculated for AuS4 and AuS3 adsorbing one O2 and H2O molecules, respectively. The adsorption capacity of AuS3 for both gas molecules is higher than AuS4, and AuSn (n = 3, 4) clusters are more favor to adsorb O2 than H2O.

Photoelectron spectroscopy of [Mo6X14]2- dianions (X = Cl-I).

Photoelectron spectroscopy and theoretical investigations have been performed to systematically probe the intrinsic electronic properties of [Mo6X14]2- (X = halogen). All three PE spectra of gaseous [Mo6X14]2- (X = Cl, Br, I) dianions, which were generated by electrospray ionization, exhibit multiple resolved peaks in the recorded binding energy range. Theoretical investigations on the orbital structure and charge distribution were performed to support interpretation of the observed spectra and were further extended onto [Mo6F14]2-, a dianion that was not available for the experimental study. The measured adiabatic (ADE) and vertical detachment energies (VDE) for X = Cl-I were well reproduced by density functional theory calculations (accuracy ∼0.1 eV). Corresponding ADE/VDE values for the dianions were found to be 1.48/2.13 (calc.) and 2.30/2.65, 2.30/2.62, and 2.20/2.42 eV (all expt.) for X = F, Cl, Br, and I, respectively, showing an interesting buckled trend of electron binding energy (EBE) along the halogen series, i.e., EBE (F) ≪ EBE (Cl) ∼ EBE (Br) > EBE (I). Molecular orbital analyses indicate different mixing of metal and halogen atomic orbitals, which is strongly dependent on the nature of X, and suggest that the most loosely bound electrons are detached mainly from the metal core for X = F and Cl, but from halide ligands for X = Br and I. The repulsive Coulomb barrier (RCB), estimated from the photon energy dependent spectra, decreases with increasing halogen size, from 1.8 eV for X = Cl to 1.6 eV for X = I. Electrostatic potential modeling confirms the experimental RCB values and predicts that the most favorable electron detaching pathway should lie via the face-bridging halide ligands.

Electronic surface, optical and electrical properties of p – GaN activated via in-situ MOCVD and ex-situ thermal annealing in InGaN/GaN LED

Electronic surface properties, optical and electrical characteristics of p-type Mg-doped Gallium Nitride (p-GaN) activated under different thermal annealing condition were investigated. In this work, p-GaN samples were subjected to in-situ and ex-situ thermal annealing process at 650 °C in Nitrogen (N2) rich condition. In-situ annealing process took place in Metal Oxide Chemical Vapor Deposition (MOCVD) chamber while ex-situ annealing process was carried out in the conventional oven. X-Ray and Ultraviolet Photoemission Spectroscopy (XPS/UPS) were used to observe the energy alignment of the p-GaN surface. From PES spectra, the sample subjected to in-situ thermal annealing shown to exhibit lower surface bend bending of 0.28 eV as compared to ex-situ thermal annealing activation with 0.45 eV band bending. This result is in agreement with specific contact resistance measurement that shows in-situ sample exhibits lower resistance resulted in better carrier injection from metal to p-GaN. Photoluminescence (PL) spectra elucidates that in-situ sample has a good surface quality with less nitrogen related vacancies (VN) formed on the p-GaN surface. All these results are further proved with the higher output power from LED with in-situ annealing. At 20 mA, in-situ sample shown an increment of ~14% light output power compared to ex-situ sample. Results obtained in this work suggest that the thermal activation condition for p-GaN activation process plays an active role on the surface quality as well as the energy alignment of the film surface and shows the potential of in-situ p-GaN activation for tunnel junction structure.

Planar B41- and B42- clusters with double-hexagonal vacancies.

Since the discovery of the B40 borospherene, research interests have been directed to the structural evolution of even larger boron clusters. An interesting question concerns if the borospherene cages persist in larger boron clusters like the fullerenes. Here we report a photoelectron spectroscopy (PES) and computational study on the structures and bonding of B41- and B42-, the largest boron clusters characterized experimentally thus far. The PE spectra of both clusters display broad and complicated features, suggesting the existence of multiple low-lying isomers. Global minimum searches for B41- reveal three low-lying isomers (I-III), which are all related to the planar B40- structure. Isomer II (Cs, 1A') possessing a double hexagonal vacancy is found to agree well with the experiment, while isomers I (Cs, 3A'') and III (Cs, 1A') both with a single hexagonal vacancy are also present as minor isomers in the experiment. The potential landscape of B42- is found to be much more complicated with numerous low-lying isomers (VII-XII). The quasi-planar structure VIII (C1, 2A) containing a double hexagonal vacancy is found to make major contributions to the observed PE spectrum of B42-, while the other low-lying isomers may also be present to give rise to a complicated spectral pattern. Chemical bonding analyses show isomer II of B41- (Cs, 1A') and isomer VIII of B42- (C1, 2A) are π aromatic, analogous to that in the polycyclic aromatic hydrocarbon C27H13+ (C2v, 1A1). Borospherene cage isomers are also found for both B41- and B42- in the global minimum searches, but they are much higher energy isomers.

TGMin: An efficient global minimum searching program for free and surface-supported clusters.

In this article, we introduce an efficient global-minimum structural search program named Tsinghua Global Minimum 2 (TGMin-2), which is the successor of the original TGMin algorithm that was developed in our group in 2011. We have introduced a number of new features and improvements into TGMin-2, including a symmetric structure generation algorithm that can produce good initial seeds for small- and medium-size clusters, the duplicated structure identification algorithm, and the improved structure adaption algorithm that was implemented in the original TGMin code. To predict the simulated photoelectron spectrum (PE spectrum) automatically, we also implemented a standalone program named AutoPES (Auto Photoelectron Spectroscopy), which can be used to simulate PE spectra and compare them with experimental results automatically. We have demonstrated that TGMin-2 and AutoPES are powerful tools for studying free and surface-supported molecules, clusters, and nanoclusters. © 2018 Wiley Periodicals, Inc.

Intra- and intercycle interference of angle-resolved electron emission in laser-assisted XUV atomic ionization

A theoretical study of ionization of the hydrogen atom due to an XUV pulse in the presence of an infrared (IR) laser is presented. Well-established theories are usually used to describe the laser-assisted photoelectron effect: the well-known soft-photon approximation firstly posed by Maquet et al (2007 J. Mod. Opt. 54 1847) and Kazansky’s theory in (2010 Phys. Rev. A 82, 033420). However, these theories completely fail to predict the electron emission perpendicularly to the polarization direction. Making use of a semiclassical model (SCM), we study the angle-resolved energy distribution of PEs for the case that both fields are linearly polarized in the same direction. We thoroughly analyze and characterize two different emission regions in the angle-energy domain: (i) the parallel-like region with contribution of two classical trajectories per optical cycle and (ii) the perpendicular-like region with contribution of four classical trajectories per optical cycle. We show that our SCM is able to assess the interference patterns of the angle-resolved PE spectrum in the two different mentioned regions. Electron trajectories stemming from different optical laser cycles give rise to angle-independent intercycle interferences known as sidebands. These sidebands are modulated by an angle-dependent coarse-grained structure coming from the intracycle interference of the electron trajectories born during the same optical cycle. We show the accuracy of our SCM as a function of the time delay between the IR and the XUV pulses and also as a function of the laser intensity by comparing the semiclassical predictions of the angle-resolved PE spectrum with the continuum-distorted wave strong field approximation and the ab initio solution of the time-dependent Schrödinger equation.

B26−: The smallest planar boron cluster with a hexagonal vacancy and a complicated potential landscape

Anionic boron clusters have been systematically investigated both experimentally and theoretically up to 30 atoms and have all been proved to be planar or quasi-planar (2D) in their global minima. However, the B26− cluster has remained elusive in this size range up to now, because of its complicated potential landscape. Here we present a joint photoelectron spectroscopy (PES) and first-principles study on the structures and bonding of this seemingly enigmatic cluster. Extensive global minimum searches, followed by high-level calculations and Gibbs free energy corrections, reveal that at least three 2D isomers, I (C1, 2A), II (C1, 2A), and III (C1, 2A), could contribute to the observed PE spectrum for the B26− cluster. Isomer I, which has the lowest free energy at finite temperatures, is found to dominate the experimental spectrum and represents the smallest 2D boron cluster with a hexagonal vacancy. Distinct spectral features are observed for isomer III, which has a pentagonal hole and is found to contribute to the measured PE spectrum as a minor species. Isomer II with a close-packed triangular 2D structure, which is the global minimum at 0K, may also contribute to the observed spectrum as a minor species. Chemical bonding analyses show that the principal isomer I can be viewed as an all-boron analog of the polycyclic aromatic hydrocarbon C17H11+ in terms of the π bonds.

Photoelectron Imaging Spectra of O2-·VOC and O4-·VOC Complexes.

The anion photoelectron imaging spectra of O2-·VOC and O4-·VOC (VOC = hexane, isoprene, benzene, and benzene-d6) complexes measured using 3.49 eV photon energy, along with the results of ab initio and density functional theory results are reported and analyzed. Photodetachment of these anionic complexes accesses neutrals that model collision complexes, offering a probe of the effects of symmetry-breaking collision events on the electronic structure of normally transparent neutral molecules. The energies of O2-·VOC spectral features compared to the bare O2- indicate that photodetachment of the anion accesses a modestly repulsive region of the O2-VOC potential energy surface, with subtle VOC dependence on the relative energies of the O2 (X 3Σg-)·VOC ground state and O2 (a 1Δg)·VOC excited state. In contrast, a significantly higher intensity of the transition to the O2 (a 1Δg)·VOC excited state relative to the O2 (X 3Σg-)·VOC ground state is observed for VOC = benzene, with a less pronounced effect observed for VOC = isoprene. Similar spectral effects are observed in the O4-·benzene and O4-·isoprene PE spectra. Several explanations are considered, with involvement of a temporary anion state emerging as the most plausible.

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions.

Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

Electronic structure and photoelectron spectra of nickel (II) acetylacetonate and its thio- and amino-substituted analogues

Using ultraviolet photoelectron spectroscopy and electron density functional theory (DFT), we investigated the electronic structure of the d8 complex acetylacetonate Ni(a≿а≿)2 and its NH, S and NCH2-substitutes: nickel bis(acetylacetoneiminate) (Ni(acim)2), Ni(Sacac)2 and nickel N,N′-Ethylene-bis(acetylacetoneiminate) (NiEcim), respectively. Based on the spectral regularities and calculated results for these four compounds, we interpreted the PE spectra to approximate the extended Koopmans' theorem IEi = –εi + δi using the δi relationship to the molecular orbital type, which differs substantially from earlier published interpretations. We determined the vertical ionization energies for the four pairs of ligand n- and π-levels and four d-type orbitals for the metal. We further discussed the regularities established both experimentally and theoretically for the influence that substituting S, NH and NCH2- for O exerted on the electronic and spatial structure of the complexes, effective atomic charges and intra-complex coordinate bonds.

Rotationally resolved state-to-state photoelectron study of zirconium monoxide cation (ZrO+)

Using two-colour visible (Vis)–ultraviolet (UV) photoionisation and pulsed field ionisation–photoelectron (PFI–PE) methods, we have obtained cleanly rotationally resolved photoelectron spectra for ZrO+(X 2Δ3/2,5/2; v+ = 0, 1, and 2). The rotation assignment of these state-to-state Vis–UV–PFI–PE spectra has allowed the unambiguous determination of the ground state term symmetry for ZrO+(X) to be 2Δ3/2, and the adiabatic ionisation energy of 90Zr16O, IE(90Zr16O) = 54,948.3(8) cm−1 [6.81272(10) eV]. The symmetry of the ionic ZrO+(X 2Δ3/2) ground state determined here disagrees with that reported in previous experiments. The rotational and vibrational constants determined in this experiment for the ionic 90Zr16O+(X 2Δ3/2) ground state are: Be+ = 0.4343(8) cm−1 and αe+ = 0.0019(5) cm−1, and ωe+ = 991.2(8) cm−1 and ωe+xe+ = 3.5(8) cm−1; and those for the ionic 90Zr16O+(X 2Δ5/2) excited spin-orbit state are: Be+ = 0.4357(6) cm−1 and αe+ = 0.0022(4) cm−1, and ωe+ = 991.9(8) cm−1 and ωe+xe+ = 3.6(8) cm−1, respectively. Based on the latter Be+ value, the equilibrium bond distances are determined to be re+ = 1.691(2) Å for 90Zr16O+(X 2Δ3/2) and re+ = 1.688(1) Å for 90Zr16O+(X 2Δ5/2). The IE(ZrO) along with the spectroscopic constants obtained here are valuable for benchmarking the ab initio quantum chemical calculations for energetic and structural predictions of ZrO/ZrO+.

Stable and high-power few cycle supercontinuum for 2D ultrabroadband electronic spectroscopy.

Broadband supercontinuum (SC) pulses in the few cycle regime are a promising source for spectroscopic and imaging applications. However, SC sources are plagued by poor stability, greatly limiting their utility in phase-resolved nonlinear experiments such as 2D photon echo spectroscopy (2D PES). Here, we generated SC by two-stage filamentation in argon and air starting from 100fs input pulses, which are sufficiently high-power and stable to record time-resolved 2D PE spectra in a single laser shot. We obtain a total power of 400μJ/pulse in the visible spectral range of 500-850nm and, after compression, yield pulses with duration of 6fs according to transient-grating frequency-resolved optical gating (TG-FROG) measurements. We demonstrate the method on the laser dye, Cresyl Violet, and observe coherent oscillations indicative of nuclear wavepacket dynamics.

Ab initio and anion photoelectron study of AunRhm (n = 1-7, m = 1-2) clusters.

Anion photoelectron spectroscopy (PES) and ab initio calculations have been used to identify the unique structural, electronic, and magnetic properties of both neutral and anionic binary AunRhm (n = 1-7 and m = 1-2) clusters in vacuo. Negative ion photoelectron spectra are presented with electron binding energies measured up to 3.493 eV. We discuss our computational results in the context of the PES experiment, in which the calculated electron affinities and vertical detachment energies are in good agreement with the measured values. Theoretically, we investigate the low-lying energy structures and the spin isomers of each neutral, anionic and cationic species. The PES spectra, binding energies, fragmentation energy, electron affinities, vertical and adiabatic detached energies, HOMO-LUMO (H-L) gaps and vibrational spectra are presented and discussed. Our results show that the characteristic planarity for gold clusters is preserved for many of the bimetallic clusters. This study is therefore compared with the case of pure gold for which ample experimental and theoretical data are available. Both experimental and theoretical results obtained here are compared and discussed with previous theoretical studies on the same systems.