Photoelectron spectra of the MX2− (M=Li, Na; X=Cl, Br, I) superhalogen anions have been obtained for the first time. The first vertical detachment energies (VDEs) were measured to be 5.92±0.04 (LiCl2−), 5.86±0.06 (NaCl2−), 5.42±0.03 (LiBr2−), 5.36±0.06 (NaBr2−), 4.88±0.03 (LiI2−), and 4.84±0.06 eV (NaI2−), which are all well above the 3.61 eV electron detachment energy of Cl−, the highest among atomic anions. Experimental photoelectron spectra have been assigned on the basis of ab initio outer valence Green function (OVGF) calculations. The corresponding theoretical first VDEs were found to be 5.90 (LiCl2−), 5.81 (NaCl2−), 5.48 (LiBr2−), 5.43 (NaBr2−), 4.57 (LiI2−), and 4.50 eV (NaI2−), in excellent agreement with the experimental values. Photodetachment from the top four valence molecular orbitals (2σg22σu21πu41πg4) of MX2− was observed. Analysis of the polestrength showed that all electron detachment channels in this study can be described as primarily one-electron processes.

Valence electron

10.1063/1.478386

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Citations (289)

Electronic and Structural Evolution and Chemical Bonding in Ditungsten Oxide Clusters: W₂O_n^- and W₂O_n (n = 1−6)

The Journal of Physical Chemistry A (2005)

Hua‐Jin Zhai Xin Huang Lifeng Cui Xi Li Jun Li

We report a systematic and comprehensive investigation of the electronic structures and chemical bonding in a series of ditungsten oxide clusters, W2O(n)- and W2O(n) (n = 1-6), using anion photoelectron spectroscopy and density functional theory (DFT) calculations. Well-resolved photoelectron spectra were obtained at several photon energies (2.331, 3.496, 4.661, 6.424, and 7.866 eV), and W 5d-based spectral features were clearly observed and distinguished from O 2p-based features. More complicated spectral features were observed for the oxygen-deficient clusters because of the W 5d electrons. With increasing oxygen content in W2O(n)-, the photoelectron spectra were observed to shift gradually to higher binding energies, accompanied by a decreasing number of W 5d-derived features. A behavior of sequential oxidation as a result of charge transfers from W to O was clearly observed. A large energy gap (2.8 eV) was observed in the spectrum of W2O6-, indicating the high electronic stability of the stoichiometric W2O6 molecule. Extensive DFT calculations were carried out to search for the most stable structures of both the anion and neutral clusters. Time-dependent DFT method was used to compute the vertical detachment energies and compare to the experimental data. Molecular orbitals were used to analyze the chemical bonding in the ditungsten oxide clusters and to elucidate their electronic and structural evolution.

Stoichiometry

10.1021/jp051496f

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Citations (70)

Pb₁₂^2-: Plumbaspherene

The Journal of Physical Chemistry A (2006)

Lifeng Cui Xin Huang Lei‐Ming Wang Jun Li Lai‐Sheng Wang

Although Si or Ge is not known to form empty cage clusters such as the fullerenes, we recently found a unique 12-atom icosahedral tin cluster, Sn12 2- (stannaspherene). Here we report photoelectron spectroscopy and theoretical evidence that Pb12 2- is also a highly stable icosahedral cage cluster and bonded by four delocalized radial pi bonds and nine delocalized on-sphere sigma bonds from the 6p orbitals of the Pb atoms. Following Sn12 2-, we coin a name, plumbaspherene, for the highly stable and nearly spherical Pb12 2- cluster, which is expected to be stable in solution and the solid state. Plumbaspherene has a diameter of approximately 6.3 A with an empty interior volume large enough to host most transition metal atoms, affording a new class of endohedral clusters.

10.1021/jp063617x

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Citations (129)

Transition-metal-like bonding behaviors of a boron atom in a boron-cluster boronyl complex [(η⁷-B₇)-B-BO]⁻

Chemical Science (2021)

Wen‐Juan Tian Weijia Chen Miao Yan Rui Li Zhihong Wei

The global minimum of the B₉O⁻ cluster is found to have an umbrella-like structure, where the central B atom exhibits transition-metal-like bonding properties, coordinated by a η⁷-B₇ ligand on one side and a BO ligand on the other.

BORO

10.1039/d1sc00534k

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Probing the Electronic Structure of [2Fe-2S] Clusters with Three Coordinate Iron Sites by Use of Photoelectron Spectroscopy

The Journal of Physical Chemistry A (2005)

You‐Jun Fu Xin Yang Xue‐Bin Wang Lai‐Sheng Wang

Five series of [2Fe-2S] complexes, [Fe2S2Cl2-x(CN)x]-, [Fe2S2(SEt)2-xClx]-, [Fe2S2(SEt)2-x(CN)x]-, [Fe2S2Cl2-x(OAc)x]- (OAc = acetate), and [Fe2S2(SEt)2-x(OPr)x]- (OPr = propionate) (x = 0−2), were produced by collision-induced dissociation of the corresponding [4Fe-4S] complexes, and their electronic structures were studied by photoelectron spectroscopy. All the [2Fe-2S] complexes contain a [Fe2S2]+ core similar to that in reduced [2Fe] ferredoxins but with different coordination geometries. For the first three series, which only involve tricoordinated Fe sites, a linear relationship between the measured binding energies and the substitution number (x) was observed, revealing the independent ligand contributions to the total electron binding energies. The effect of the ligand increases in the order SEt → Cl → CN, conforming to their electron-withdrawing ability in the same order. The carboxylate ligands in the [Fe2S2Cl2-x(OAc)x]- and [Fe2S2(SEt)2-x(OPr)x]- complexes were observed to act as bidentate ligands, giving rise to tetracoordinated iron sites. This is different from their monodentate coordination behavior in the [4Fe-4S] cubane complexes, reflecting the high reactivity of the unsatisfied three-coordinate iron site in the [2Fe-2S] complexes. The [2Fe-2S] complexes with tetracoordinated iron sites exhibit lower electron binding energies, that is, higher reductive activity than the all tricoordinate planar clusters. The electronic structures of all the [2Fe-2S] complexes were shown to conform to the "inverted energy level scheme".

Reactivity

10.1021/jp045177k

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Citations (14)

Diversity of Functionalized Germanium Zintl Clusters: Syntheses and Theoretical Studies of [Ge9PdPPh3]3− and [Ni@(Ge9PdPPh3)]2−

Journal of Cluster Science (2009)

Zhong‐Ming Sun Ya‐Fan Zhao Jun Li Lai‐Sheng Wang

Bimetallic strip

Ethylene diamine

Nanochemistry

10.1007/s10876-009-0266-1

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Citations (36)

Photoelectron spectroscopy of small chromium clusters: Observation of even-odd alternations and theoretical interpretation

Physical review. B, Condensed matter (1997)

Lai‐Sheng Wang Hongbin Wu Hansong Cheng

We report an extensive photoelectron-spectroscopy study of size-selected ${\mathrm{Cr}}_{\mathrm{n}}^{\mathrm{\ensuremath{-}}}$ (n=2--70) clusters. Even-odd alternations are observed for the small ${\mathrm{Cr}}_{\mathrm{n}}$ clusters and their electron affinities. The spectra of clusters with an even number of atoms show less density of states near the threshold, while those with odd clusters show more complex features. A dimer growth path found in a previous theoretical study is used to interpret the data and accounts well for the even-odd effects. The work provides a key contribution to the understanding of the complicated electronic structure of the Cr clusters.

Electron spectroscopy

10.1103/physrevb.55.12884

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Citations (48)

A combined density functional theoretical and photoelectron spectroscopic study of Ge2O2

The Journal of Chemical Physics (1995)

John B. Nicholas Jiawen Fan Hongbin Wu Steve D. Colson Lai‐Sheng Wang

We study Ge2O2 and Ge2O−2 with density functional theory (DFT) and photoelectron spectroscopy (PES). We find that Ge2O2 is a rhombus (D2h), closed-shell molecule with a large HOMO-LUMO gap. The PES spectrum of Ge2O−2 is obtained at four detachment photon energies: 1064, 532, 355, and 266 nm. Vibrational structure is resolved at the lowest photon energy with a single progression and a frequency of 400 (60) cm−1. The experimental adiabatic electron affinity is obtained to be 0.625 (0.050) eV for Ge2O2. The calculated vertical and adiabatic electron affinities and the HOMO-LUMO gap are in good agreement with the experimental values. The calculated totally symmetric vibrational mode of Ge2O2 (335 cm−1) is in reasonable agreement with the observed vibration and represents a Ge–Ge breathing motion.

HOMO/LUMO

10.1063/1.468959

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Citations (26)