Xiaopeng Xing

Evidence of Significant Covalent Bonding in Au(CN)2

The Au(CN)(2)(-) ion is the most stable Au compound known for centuries, yet a detailed understanding of its chemical bonding is still lacking. Here we report direct experimental evidence of significant covalent bonding character in the Au-C bonds in Au(CN)(2)(-) using photoelectron spectroscopy and comparisons with its lighter congeners, Ag(CN)(2)(-) and Cu(CN)(2)(-). Vibrational progressions in the Au-C stretching mode were observed for all detachment transitions for Au(CN)(2)(-), in contrast to the atomic-like transitions for Cu(CN)(2)(-), revealing the Au-C covalent bonding character. In addition, rich electronic structural information was obtained for Au(CN)(2)(-) by employing 118 nm detachment photons. Density functional theory and high-level ab initio calculations were carried out to understand the photoelectron spectra and obtain insight into the nature of the chemical bonding in the M(CN)(2)(-) complexes. Significant covalent character in the Au-C bonding due to the strong relativistic effects was revealed in Au(CN)(2)(-), consistent with its high stability.

Photoelectron spectroscopy of anions at 118.2nm: Observation of high electron binding energies in superhalogens MCl4− (M=Sc, Y, La)

High energy photon is needed for photoelectron spectroscopy (PES) of anions with high electron binding energies, such as superhalogens and O-rich metal oxide clusters. The highest energy photon used for anion PES in the laboratory has been 157 nm (7.866 eV) from F2 eximer lasers. Here, we report an anion PES experiment using coherent vacuum ultraviolet radiation at 118.2 nm (10.488 eV) by tripling the third harmonic output (355 nm) of a Nd:YAG laser in a XeAr cell. Our study focuses on a set of superhalogen species, MCl(4) (-) (M=Sc, Y, La), which were expected to possess very high electron binding energies. While the 157 nm photon can only access the ground state detachment features for these species, more transitions to the excited states at binding energies higher than 8 eV are observed at 118.2 nm. The adiabatic detachment energies are shown to be, 6.84, 7.02, and 7.03 eV for ScCl(4) (-), YCl(4) (-), and LaCl(4) (-) eV, respectively, whereas their corresponding vertical detachment energies are measured to be 7.14, 7.31, and 7.38 eV.

Infrared Photodissociation Spectroscopy of Mononuclear Iron Carbonyl Anions

The infrared photodissociation spectroscopy of mass-selected mononuclear iron carbonyl anions Fe(CO)(n)(-) (n = 2-8) were studied in the carbonyl stretching frequency region. The FeCO(-) anion does not fragment when excited with infrared light. Only a single IR active band was observed for the Fe(CO)(2)(-) and Fe(CO)(3)(-) anions, consistent with theoretical predictions that these complexes have linear D(∞h) and planar D(3h) symmetry, respectively. The Fe(CO)(4)(-) anion is the most intense peak in the mass spectra and was characterized to have a completed coordination sphere with high stability. Anion clusters larger than n = 4 were determined to involve a Fe(CO)(4)(-) core anion that is progressively solvated by external CO molecules. Three CO stretching vibrational fundamentals were observed for the Fe(CO)(4)(-) core anion, indicating that the Fe(CO)(4)(-) anion has a C(3v) structure. All the carbonyl stretching frequencies of the Fe(CO)(n)(-) anion complexes are red-shifted with respect to those of the corresponding neutrals.

Photoelectron Imaging and Spectroscopy of MI2- (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding

We report a combined experimental and theoretical investigation of MI(2)(-) (M = Cs, Cu, Ag, Au) to explore the chemical bonding in the group IA and IB diiodide complexes. Both photoelectron imaging and low-temperature photoelectron spectroscopy are applied to MI(2)(-) (M = Cs, Cu, Au), yielding vibrationally resolved spectra for CuI(2)(-) and AuI(2)(-) and accurate electron affinities, 4.52 ± 0.02, 4.256 ± 0.010, and 4.226 ± 0.010 eV for CsI(2), CuI(2), and AuI(2), respectively. Spin-orbit coupling is found to be important in all the diiodide complexes and ab initio calculations including spin-orbit effects allow quantitative assignments of the observed photoelectron spectra. A variety of chemical bonding analyses (charge population, bond order, and electron localization functions) have been carried out, revealing a gradual transition from the expected ionic behavior in CsI(2)(-) to relatively strong covalent bonding in AuI(2)(-). Both relativistic effects and electron correlation are shown to enhance the covalency in the gold diiodide complex.

Photoelectron Spectroscopy of Cold Hydrated Sulfate Clusters, SO42-(H2O)N ((N = 4-7): Temperature-Dependent Isomer Populations

Sulfate is an important inorganic anion and its interactions with water are essential to understand its chemistry in aqueous solution. Studies of sulfate with well-controlled solvent numbers provide molecular-level information about the solute-solvent interactions and critical data to test theoretical methods for weakly bounded species. Here we report a low-temperature photoelectron spectroscopy study of hydrated sulfate clusters SO(4)(2-)(H(2)O)(n) (n = 4-7) at 12 K and ab initio studies to understand the structures and dynamics of these unique solvated systems. A significant increase of electron binding energies was observed for the 12 K spectra relative to those at room temperature, suggesting different structural isomers were populated as a function of temperature. Theoretical calculations revealed a competition between isomers with optimal water-solute and water-water interactions. The global minimum isomers all possess higher electron binding energies due to their optimal water-solute interactions, giving rise to the binding energy shift in the 12 K spectra, whereas many additional low-lying isomers with less optimal solvent-solute interactions were populated at room temperature, resulting in a shift to lower electron binding energies in the observed spectra. The current work demonstrates and confirms the complexity of the water-sulfate potential energy landscape and the importance of temperature control in studying the solvent-solute systems and in comparing calculations with experiment.

Infrared photodissociation spectra of mass selected homoleptic dinuclear iron carbonyl cluster anions in the gas phase

Infrared spectra of mass-selected homoleptic dinuclear iron carbonyl cluster anions Fe2(CO)n− (n = 4–9) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The cluster anions are produced via a laser vaporization supersonic cluster source. Density functional calculations have been performed and the calculated vibrational spectra are compared to the experimental data to identify the gas-phase structures of the cluster anions. The experimentally observed Fe2(CO)n− (n = 4–7) cluster anions are characterized to have unusual asymmetric (OC)4Fe–Fe(CO)n−4 structures, which also correspond to the computed lowest energy structures. The experimentally observed Fe2(CO)8− cluster anion is determined to have an unbridged structure instead of the previously reported dibridged structure. The Fe2(CO)9− cluster anion is determined to involve a Fe2(CO)8− core anion that is solvated by an external CO molecule. Bonding analysis indicates that these anions each have a Fe–Fe single bond to satisfy the 18-electron configuration of one iron center. The results provide important new insight into the structure and bonding mechanisms of transition-metal carbonyl clusters.

Bonding in homoleptic iron carbonyl cluster cations: a combined infrared photodissociation spectroscopic and theoretical study

Infrared spectra of mass-selected homoleptic iron carbonyl cluster cations including mononuclear Fe(CO)5+ and Fe(CO)6+, dinuclear Fe2(CO)8+ and Fe2(CO)9+, and trinuclear Fe3(CO)12+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. Only one IR band is observed for the Fe(CO)5+ cation, which is predicted to have a C4v structure. The Fe(CO)6+ cation is determined to be a weakly bound complex involving a Fe(CO)5+ core ion. In contrast to neutral clusters which have symmetric structures with two and three bridging carbonyl ligands, the dinuclear Fe2(CO)8+ and Fe2(CO)9+ cations are characterized to have unbridged asymmetric (OC)5Fe–Fe(CO)n+ (n = 3 and 4) structures. The trinuclear Fe3(CO)12+ cluster cation is determined to have an open chain like (OC)5Fe–Fe(CO)2–Fe(CO)5 structure instead of the triangular structure with two bridging CO groups for the Fe3(CO)12 neutral. The di- and trinuclear cluster cations all involve a square pyramid like Fe(CO)5 building block that satisfies the 18-electron configuration of this iron center. The Fe(CO)5 building block is isolobal to the CH3 fragment in hydrocarbon chemistry, the Fe2(CO)9+ and Fe3(CO)12+ cluster cations may be considered through isolobality to be metal carbonyl analogues of the ethyl and isopropyl cations.

Observation of H2 aggregation onto a doubly charged anion in a temperature-controlled ion trap.

Hydrogen is the second most difficult gas to be condensed due to its weak intermolecular interactions. Here we report observation of H(2) aggregation onto a doubly charged anion, (-)O(2)C(CH(2))(12)CO(2)(-)(DC(2-)). Weakly bound DC(2-)(H(2))(n) clusters were formed in a temperature-controlled ion trap and studied using photoelectron spectroscopy. The onset of clustering was observed at 30 K, whereas extensive condensation was observed at 12 K with n up to 12. Photoelectron spectra were obtained for DC(2-)(H(2))(n) (n = 0-6) at 193 and 266 nm. The spectra of DC(2-)(H(2))(n) were observed to be identical to that of the bare DC(2-) dianion except a slight blue shift, indicating the weak interactions between H(2) and the parent dianion. The blue shift on average amounts to approximately 34 meV (3.3 kJ/mol) per H(2), which represents the lower limit of the H(2) binding energy to DC(2-).

Structures and properties the lead-doped carbon clusters PbCn/PbCn+/PbCn- (n=1-10)

A systemic density functional theory study of the lead-doped carbon clusters PbCn/PbCn+/PbCn− (n=1–10) has been carried out using B3LYP method with both CEP-31G and TZP+ basis sets. For each species, the electronic states, relative energies and geometries of various isomers are reported. According to these calculations, the Pb-terminated linear or quasilinear isomer is the most stable structure for PbCn/PbCn+/PbCn− clusters except for PbC2/PbC2+ and PbC10/PbC10+. Both PbC2 and PbC2+ have bent ground state structure. For neutral PbC10, the global minimum possesses a Pb-containing 11-membered ring structure, while for cationic PbC10+, the Pb-side-on C10 monocyclic configuration has lowest energy. Except for the smallest PbC, PbC+, and PbC−, the electronic ground state is alternate between 3Σ (for n-odd member) and 1Σ (for the n-even member) for linear PbCn and invariably 2Π for linear PbCn+ and PbCn−. The incremental binding energy diagrams show that strong even–odd alternations in the cluster stability exi...

Photoelectron imaging of doubly charged anions, (-)O2C(CH2)nCO2(-) (n = 2-8): observation of near 0 eV electrons due to secondary dissociative autodetachment.

The hallmark of multiply charged anions is the repulsive Coulomb barrier (RCB), which prevents low-energy electrons from being emitted in photodetachment experiments. However, using photoelectron imaging, we have observed persistent near 0 eV electrons during photodetachment of doubly charged dicarboxylate anions, (-)O(2)C(CH(2))(n)CO(2)(-) (D(n)(2-), n = 2-8). Here we show that these low-energy electron signals are well structured and are independent of the detachment photon fluxes or energies. The relative intensities of these signals are dependent on n, with maxima at n = 2, 4, and 6. These near 0 eV electrons cannot come from direct photodetachment of the dianions and are proposed to come from decarboxylation of the product radical anions upon photodetachment of the parent dianions [(*)O(2)C(CH(2))(n)CO(2)(-) --> CO(2) + (*)(CH(2))(n)CO(2)(-)], followed by dissociative autodetachment [(*)(CH(2))(n)CO(2)(-) --> (CH(2))(n) + CO(2) + e] or hydrogen-transfer-induced electron detachment [(*)(CH(2))(n)CO(2)(-) --> CH(2)=CH(CH(2))(n-2)CO(2)H + e]. Energetic considerations suggest that these processes are exothermic. It is further observed that solvation by one water molecule quenches the low-energy electron signals in the spectra of D(n)(2-)(H(2)O), consistent with the proposed mechanisms. These indirect dissociative autodetachment processes are expected to involve cyclic transition states for n > 2, which is in agreement with the dependence on the chain length due to the anticipated strains in the intermediate steps. The quenching of the low-energy electron signals by one water molecule demonstrates the importance of solvation on chemical reactions.