Gas-phase Photoelectron Spectroscopy Research Articles

Effect of total charge on the electronic structure of thiolate-protected X@Ag12 superatoms (X = Ag, Au).

Electronic structures of chemically synthesized silver-based clusters [XAg16(TBBT)12]3- (X = Ag or Au; TBBT = 4-tert-butylbenzenethiolate) having an icosahedral X@Ag12 superatomic core were studied by gas-phase photoelectron spectroscopy and density functional theory calculations. The electron binding energy of the highest occupied molecular orbital (HOMO) with a 1P superatomic nature was determined to be 0.23 and 0.29 eV for X = Ag or Au, respectively. Resonant tunnelling electron emission through the repulsive Coulomb barrier (RCB) was observed. From the kinetic energy of the tunnelling electrons, it was estimated that the lowest unoccupied molecular orbital (LUMO) was supported at 1.51 and 1.62 eV above the vacuum level by the RCB for X = Ag or Au, respectively. The HOMO of [XAg16(TBBT)12]3- (X = Ag or Au) was destabilized by 3.74 and 3.71 eV, respectively, compared with those of [XAg24(DMBT)18]- (DMBT = 2,4-dimethylbenzenethiolate) having the icosahedral X@Ag12 core due to the larger negative charge imparted by the ligand layers.

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 gas phase reaction of iridium and iridium carbide anions with 2-hydoxyethylhydrazine (HEH)

Understanding the chemistry of compounds that are similar to hydrazine has two advantages. First, it helps to identify less hazardous propellants to replace hydrazine as the most widely used monopropellant. And second, it helps to gain insight into the reaction mechanism that could be analogous to the decomposition of hydrazine into ammonia and nitrogen. Ionic liquids have already shown to be promising candidates to replace hydrazine. The molecule investigated in this study is 2-hydroxyethlyhydrazine (HOCH2CH2NHNH2; HEH), which is a neutral precursor to the ionic liquid 2-hydroxyethylhydrazinium nitrate (HEHN) and differs from hydrazine by the substitution of a hydrogen with a hydroxyethyl group. Gas phase photoelectron spectroscopy and density functional theory were used to examine the reaction between a HEH molecule and an Ir− anion as well as with IrC−. Suggested by the experimental and theoretical data, Ir− and IrC− react with HEH and can attack the C–N, C–O, N–N, C–H and the C–C bond in HEH.

Isoelectronic IrC3-, PtC3, and AuC3+ Clusters Featuring the Structural and Bonding Resemblance to OC3.

The IrC3- and PtC3- anions generated by laser vaporization were identified and characterized by gas-phase photoelectron spectroscopy and quantum-chemical calculations. The straight-chain structures with an MCCC (M = metal; C = carbon) connectivity are found for the isoelectronic IrC3-, PtC3, and AuC3+ clusters. Further elaborate analyses manifest the strikingly structural and bonding similarities between MC3-/0/+ clusters and OC3 revealed. This finding has broadened the notion of autogenic isolobality to the gas-phase clusters that contain Ir-, Pt, Au+, and C centers.

Critical Role of CF3 Groups in the Electronic Stabilization of [PdAu24(C≡CC6H3(CF3)2)18]2- as Revealed by Gas-Phase Anion Photoelectron Spectroscopy.

The role of alkynyl ligands with electron-withdrawing nature in the stability of metal clusters was investigated by gas-phase anion photoelectron spectroscopy (PES) on heteroleptic cluster anions [PdAu24(C≡CArF)18-x(C≡CPh)x]2- (ArF = 3,5-(CF3)2C6H3). Gas-phase PES on the cluster anions with specific x (= 0-6) revealed that electron binding energies decreased linearly with x, indicating that the electron-withdrawing CF3 substituents on the alkynyl ligand played a critical role in the electronic stabilization of [PdAu24(C≡CArF)18]2-. Density functional theory calculations reproduced the decrease of electron binding energies and rationally explained the ligand effect by a mechanism similar to the modulation of the work function of gold films by organic monolayers.

Ultrafast Transfer and Transient Entrapment of Photoexcited Mg Electron in Mg@C_{60}.

Electron relaxation is studied in endofullerene Mg@C_{60} after an initial localized photoexcitation in Mg by nonadiabatic molecular dynamics simulations. Two approaches to the electronic structure of the excited electronic states are used: (i)an independent particle approximation based on a density-functional theory description of molecular orbitals and (ii)a configuration-interaction description of the many-body effects. Both methods exhibit similar relaxation times, leading to an ultrafast decay and charge transfer from Mg to C_{60} within tens of femtoseconds. Method (i)further elicits a transient trap of the transferred electron that can delay the electron-hole recombination. Results shall motivate experiments to probe these ultrafast processes by two-photon transient absorption or photoelectron spectroscopy in gas phase, in solution, or as thin films.

Elucidating the Doping Effect on the Electronic Structure of Thiolate-Protected Silver Superatoms by Photoelectron Spectroscopy.

Gas-phase photoelectron spectroscopy (PES) was conducted on [XAg24 (SPhMe2 )18 ]- (X=Ag, Au) and [YAg24 (SPhMe2 )18 ]2- (Y=Pd, Pt), which have a formal superatomic core (X@Ag12 )5+ or (Y@Ag12 )4+ with icosahedral symmetry. PES results show that superatomic orbitals in the (Au@Ag12 )5+ core remain unshifted with respect to those in the (Ag@Ag12 )5+ core, whereas the orbitals in the (Y@Ag12 )4+ (Y = Pd, Pt) core shift up in energy by about 1.4 eV. The remarkable doping effect of a single Y atom (Y=Pd, Pt) on the electronic structure of the chemically modified (Ag@Ag12 )5+ superatom was reproduced by theoretical calculations on simplified model systems and was ascribed to 1) the weaker binding of valence electrons in Y@(Ag+ )12 compared to Ag+ @(Ag+ )12 due to the reduction in formal charge of the core potential, and 2) the upward shift of the apparent vacuum level due to the presence of a repulsive Coulomb barrier between [YAg24 (SPhMe2 )18 ]- and electron.

Unravelling the Role of an Aqueous Environment on the Electronic Structure and Ionization of Phenol Using Photoelectron Spectroscopy.

Water is the predominant medium for chemistry and biology, yet its role in determining how molecules respond to ultraviolet light is not well understood at the molecular level. Here, we combine gas-phase and liquid-microjet photoelectron spectroscopy to investigate how an aqueous environment influences the electronic structure and relaxation dynamics of phenol, a ubiquitous motif in many biologically relevant chromophores. The vertical ionization energies of electronically excited states are important quantities that govern the rates of charge-transfer reactions, and, in phenol, the vertical ionization energy of the first electronically excited state is found to be lowered by around 0.8 eV in aqueous solution. The initial relaxation dynamics following photoexcitation with ultraviolet light appear to be remarkably similar in the gas-phase and aqueous solution; however, in aqueous solution, we find evidence to suggest that solvated electrons are formed on an ultrafast time scale following photoexcitation just above the conical intersection between the first two excited electronic states.

FeFe]-Hydrogenase H-Cluster Mimics with Unique Planar μ-(SCH2 )2 ER2 Linkers (E=Ge and Sn).

Analogues of the [2Fe-2S] subcluster of hydrogenase enzymes in which the central group of the three-atom chain linker between the sulfur atoms is replaced by GeR2 and SnR2 groups are studied. The six-membered FeSCECS rings in these complexes (E=Ge or Sn) adopt an unusual conformation with nearly co-planar SCECS atoms perpendicular to the Fe-Fe core. Computational modelling traces this result to the steric interaction of the Me groups with the axial carbonyls of the Fe2 (CO)6 cluster and low torsional strain for GeMe2 and SnMe2 moieties owing to the long C-Ge and C-Sn bonds. Gas-phase photoelectron spectroscopy of these complexes shows a shift of ionization potentials to lower energies with substantial sulfur orbital character and, as supported by the computations, an increase in sulfur character in the predominantly metal-metal bonding HOMO. Cyclic voltammetry reveals that the complexes follow an ECE-type reduction mechanism (E=electron transfer and C=chemical process) in the absence of acid and catalysis of proton reduction in the presence of acid. Two cyclic tetranuclear complexes featuring the sulfur atoms of two Fe2 S2 (CO)6 cores bridged by CH2 SnR2 CH2 , R=Me, Ph, linkers were also obtained and characterized.

Photoelectron imaging spectroscopy of niobium mononitride anion NbN(.).

In this gas-phase photoelectron spectroscopy study, we present the electron binding energy spectrum and photoelectron angular distributions of NbN(-) by the velocity-map imaging technique. The electron binding energy of NbN(-) is measured to be 1.42 ± 0.02 eV from the X band maximum which defines the 0-0 transition between ground states of anion and neutral. Theoretical binding energies which are the vertical and adiabatic detachment energies are computed by density functional theory to compare them with experiment. The ground state of NbN(-) is assigned to the (2)Δ3/2 state and then the electronic transitions originating from this state into X(3)ΔΩ (Ω = 1-3), a(1)Δ2, A(3)Σ1 (-), and b(1)Σ0 (+) states of NbN are reported to interpret the spectral features. As a prospective study for catalytic materials, spectral features of NbN(-) are compared with those of isovalent ZrO(-) and Pd(-).

Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate.

Dimethyl methylphosphonate (DMMP) is one of the most widely used molecules to simulate chemical warfare agents in adsorption experiments. However, the details of the electronic structure of the isolated molecule have not yet been reported. We have directly probed the occupied valence and core levels using gas phase photoelectron spectroscopy and the unoccupied states using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Density functional theory (DFT) calculations were used to study the electronic structure, assign the spectral features, and visualize the molecular orbitals. Comparison with parent molecules shows that valence and core-level binding energies of DMMP follow trends of functional group substitution on the P center. The photoelectron and NEXAFS spectra of the isolated molecule will serve as a reference in studies of DMMP adsorbed on surfaces.

Solvents effects on charge transfer from quantum dots.

To predict and understand the performance of nanodevices in different environments, the influence of the solvent must be explicitly understood. In this Communication, this important but largely unexplored question is addressed through a comparison of quantum dot charge transfer processes occurring in both liquid phase and in vacuum. By comparing solution phase transient absorption spectroscopy and gas-phase photoelectron spectroscopy, we show that hexane, a common nonpolar solvent for quantum dots, has negligible influence on charge transfer dynamics. Our experimental results, supported by insights from theory, indicate that the reorganization energy of nonpolar solvents plays a minimal role in the energy landscape of charge transfer in quantum dot devices. Thus, this study demonstrates that measurements conducted in nonpolar solvents can indeed provide insight into nanodevice performance in a wide variety of environments.

Direct Work Function Measurement by Gas Phase Photoelectron Spectroscopy and Its Application on PbS Nanoparticles

Work function is a fundamental property of a material's surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

Heterobimetallic Cuprates Consisting of a Redox‐Switchable, Silicon‐Based Metalloligand: Synthesis, Structures, and Electronic Properties

A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon-based metalloligand [κ(3)N-Si(3,5-Me2pz)3Mo(CO)3](-) is presented (pz = pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5-dimethylpyrazolyl)silanide ({Si(3,5-Me2pz)3}(-)) with [Mo(CO)3(η(6)-toluene)]. The compound features a fac-coordinated tripodal chelating ligand and an outward pointing, "free" pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ-κ(1)Si:κ(3)N-Si(3,5-Me2pz)3Mo(CO)3}](-) (X = Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X-ray diffraction analysis, electrospray mass spectrometry, infrared-induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas-phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two-coordinate copper(I) entities with the shortest silicon-copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at E(1/2)(0( = -0.60 and -0.44 V (vs. ferrocene/ferrocenium (Fc/Fc(+))), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo(0)/Mo(I) redox couple.

Photoelectron Spectroscopy of CdSe Nanocrystals in the Gas Phase: A Direct Measure of the Evanescent Electron Wave Function of Quantum Dots

We present the first photoelectron spectroscopy measurements of quantum dots (semiconductor nanocrystals) in the gas phase. By coupling a nanoparticle aerosol source to a femtosecond velocity map imaging photoelectron spectrometer, we apply robust gas-phase photoelectron spectroscopy techniques to colloidal quantum dots, which typically must be studied in a liquid solvent or while bound to a surface. Working with a flowing aerosol of quantum dots offers the additional advantages of providing fresh nanoparticles for each laser shot and removing perturbations from bonding with a surface or interactions with the solvent. In this work, we perform a two-photon photoionization experiment to show that the photoelectron yield per exciton depends on the physical size of the quantum dot, increasing for smaller dots. Next, using effective mass modeling we show that the extent to which the electron wave function of the exciton extends from the quantum dot, the so-called "evanescent electron wavefunction", increases as the size of the quantum dot decreases. We show that the photoelectron yield is dominated by the evanescent electron density due to quantum confinement effects, the difference in the density of states inside and outside of the quantum dots, and the angle-dependent transmission probability of electrons through the surface of the quantum dot. Therefore, the photoelectron yield directly reflects the fraction of evanescent electron wave function that extends outside of the quantum dot. This work shows that gas-phase photoelectron spectroscopy is a robust and general probe of the electronic structure of quantum dots, enabling the first direct measurements of the evanescent exciton wave function.

Comparison of S and Se dichalcogenolato [FeFe]-hydrogenase models with central S and Se atoms in the bridgehead chain

In order to study the influence of sulfur and selenium atoms incorporated into the structure of complexes that model the active site of [FeFe]-hydrogenases, a series of diiron dithiolato and diselenolato complexes of the form (μ-ECH2XCH2E-μ)Fe2(CO)6 have been prepared and characterized, where the diiron bridging atoms E are S or Se, and the linker bridgehead X is CH2, S, or Se. The electron energies have been compared by gas-phase photoelectron spectroscopy, and the oxidation, and reduction behaviors, as well as the ability to reduce protons from acetic acid to form H2, have been compared by cyclic voltammetry. Density functional theory computations agree well with the structures and electron energies of these molecules, and shed additional light on the oxidation and reduction properties. The computations indicate that the HOMO of each molecule where the bridgehead X is S or Se contains substantial chalcogen ‘lone pair’ orbital character. The presence of the bridgehead chalcogen lone pairs favors the Fe(CO)3 ‘rotated’ structures for both the cations and dianions of these complexes, but in different ways. In the cations one Fe(CO)3 rotates to put one carbonyl ligand in a semibridging position, and the bridgehead chalcogen lone pair electrons donate to the vacant coordination site created on the iron to stabilize the positive charge. In the dianions one Fe(CO)3 rotates to put one carbonyl ligand in a fully bridging position, and one bridging chalcogen atom breaks its bond with an iron atom, pulling the bridgehead chalcogen lone pair away from the iron to minimize the electron–electron repulsions.

Understanding Rubredoxin Redox Sites by Density Functional Theory Studies of Analogues

Determining the redox energetics of redox site analogues of metalloproteins is essential in unraveling the various contributions to electron transfer properties of these proteins. Since studies of the [4Fe-4S] analogues show that the energies are dependent on the ligand dihedral angles, broken symmetry density functional theory (BS-DFT) with the B3LYP functional and double-ζ basis sets calculations of optimized geometries and electron detachment energies of [1Fe] rubredoxin analogues are compared to crystal structures and gas-phase photoelectron spectroscopy data, respectively, for [Fe(SCH(3))(4)](0/1-/2-), [Fe(S(2)-o-xyl)(2)](0/1-/2-), and Na(+)[Fe(S(2)-o-xyl)(2)](1-/2-) in different conformations. In particular, the study of Na(+)[Fe(S(2)-o-xyl)(2)](1-/2-) is the only direct comparison of calculated and experimental gas phase detachment energies for the 1-/2- couple found in the rubredoxins. These results show that variations in the inner sphere energetics by up to ∼0.4 eV can be caused by differences in the ligand dihedral angles in either or both redox states. Moreover, these results indicate that the protein stabilizes the conformation that favors reduction. In addition, the free energies and reorganization energies of oxidation and reduction as well as electrostatic potential charges are calculated, which can be used as estimates in continuum electrostatic calculations of electron transfer properties of [1Fe] proteins.

Substituent Effects on the Electronic Characteristics of Pentacene Derivatives for Organic Electronic Devices: Dioxolane-Substituted Pentacene Derivatives with Triisopropylsilylethynyl Functional Groups

The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]-pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.

A Study of the Atmospherically Important Reactions between Dimethyl Selenide (DMSe) and Molecular Halogens (X2 = Cl2, Br2, and I2) with ab initio Calculations

The atmospherically relevant reactions between dimethyl selenide (DMSe) and the molecular halogens (X(2) = Cl(2), Br(2), and I(2)) have been studied with ab initio calculations at the MP2/aug-cc-pVDZ level of theory. Geometry optimization calculations showed that the reactions proceed from the reagents to the products (CH(3)SeCH(2)X + HX) via three minima, a van der Waals adduct (DMSe:X(2)), a covalently bound intermediate (DMSeX(2)), and a product-like complex (CH(3)SeCH(2)X:HX). The computed potential energy surfaces are used to predict what molecular species are likely to be observed in spectroscopic experiments such as gas-phase photoelectron spectroscopy and infrared matrix isolation spectroscopy. It is concluded that, for the reactions of DMSe with Cl(2) and Br(2), the covalent intermediate should be seen in spectroscopic experiments, whereas, in the DMSe + I(2) reaction, the van der Waals adduct DMSe:I(2) should be observed. Comparison is made with previous related calculations and experiments on dimethyl sulfide (DMS) with molecular halogens. The relevance of the results to atmospheric chemistry is discussed. The DMSeX(2) and DMSe:X(2) intermediates are likely to be reservoirs of molecular halogens in the atmosphere which will lead on photolysis to ozone depletion.

On the Molecular and Electronic Structures of AsP3and P4

The molecular and electronic structures of AsP(3) and P(4) have been investigated. Gas-phase electron diffraction studies of AsP(3) have provided r(g) bond lengths of 2.3041(12) and 2.1949(28) A for the As-P interatomic distances and the P-P interatomic distances, respectively. The gas-phase electron diffraction structure of P(4) has been redetermined and provides an updated value of 2.1994(3) A for the P-P interatomic distances, reconciling conflicting literature values. Gas-phase photoelectron spectroscopy provides experimental values for the energies of ionizations from the valence molecular orbitals of AsP(3) and P(4) and shows that electronically AsP(3) and P(4) are quite similar. Solid-state (75)As and (31)P NMR spectroscopy demonstrate the plastic nature of AsP(3) and P(4) as solids, and an extreme upfield (75)As chemical shift has been confirmed for the As atom in AsP(3). Finally, quantum chemical gauge-including magnetically induced current calculations show that AsP(3) and P(4) can accurately be described as strongly aromatic. Together these data provide a cohesive description of the molecular and electronic properties of these two tetraatomic molecules.