Small silicon oxide clusters: chains and rings

We study several silicon oxide cluster series with different Si:O stoichiometries using photoelectron spectroscopy (PES) of size-selected anions: (SiO)n− (n=3–5), (SiO2)n− (n =1–4), and Si(SiO2)n− (n = 2,3). The (SiO)n clusters are shown to be closed-shell molecules and the HOMOLUMO gaps are observed from the PES spectra to decrease for larger n. These clusters are shown to have ring sturctures. Si3O4 is known to have a D2d structure with two perpendicular Si2O2 rhombuses.The PES spectrum of Si4O6− is very similar to that of Si3O4−. It is concluded that Si4O6 has a similar structure with a chain of three Si2O2 rhombuses. The (SiO2)n clusters all exhibit high electron affinities and only one band is observed at 4.66 eV photon energy. These clusters are shown to have similar chain structures containing Si2O2 rhombuses, but the two terminal Si atoms are bonded to an extra 0 atom each. The possibility of using these clusters to provide structural models for oxygen-deficient defects in bulk silicon oxides is also discussed.

[1]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[2]  J. S. Anderson,et al.  Matrix Isolation Studies of Group IV Oxides. IV. Infrared Spectra and Structures of PbO, Pb2O2, and Pb4O4 , 1969 .

[3]  D. Stranz,et al.  A spectroscopic study of intermediates in the condensation of refractory smokes: Matrix isolation experiments of SiO , 1981 .

[4]  K. Raghavachari,et al.  Abinitio quantum chemical study of the dimerization of silicon monoxide , 1984 .

[5]  C. R. Helms,et al.  The physics and chemistry of SiO[2] and the Si-SiO[2] interface , 1988 .

[6]  C. R. Helms,et al.  The Physics and Chemistry of SiO2 and the Si-SiO2 Interface 2 , 1988 .

[7]  Y. Hama,et al.  2.7-eV luminescence in as-manufactured high-purity silica glass. , 1989, Physical review letters.

[8]  T. Mehner,et al.  Structure of silicon monoxide dimer: a comparison between aluminum monofluoride dimer, silicon monoxide dimer, and phosphorus mononitride dimer. Matrix infrared investigation and ab initio calculation , 1989 .

[9]  H. Schnöckel,et al.  Dimeres SiO2 Matrix‐IR‐Untersuchungen und ab initio SCF‐Rechnungen , 1990 .

[10]  C. Blancard,et al.  Probing matrix isolated SiO molecular clusters by X-ray absorption spectroscopy , 1991 .

[11]  Semiempirical calculations of point defects in silica. Oxygen vacancy and twofold coordinated silicon atom , 1992 .

[12]  M. Pelino,et al.  Ab initio study on the Al2O, Al2O2, Si2O2 and AlSiO2 oxides and on the LiAlO2 and NaAlO2 molecules , 1992 .

[13]  Linards Skuja,et al.  Isoelectronic series of twofold coordinated Si, Ge, and Sn atoms in glassy SiO2: a luminescence study , 1992 .

[14]  J. Simons,et al.  Ab initio study of the silicon oxide (Si2O and Si3O) molecules , 1993 .

[15]  V. Sulimov,et al.  Theory of Twofold Coordinated Silicon and Germanium Atoms in Solid Silicon Dioxide , 1994 .

[16]  Introduction to food engineering, 2nd edition: By R. Paul Singh and Dennis R. Heldman. Academic Press Inc., London, 1993. xi + 499 pp. ISBN 0-12-646381-6. Price: £42.00 , 1994 .

[17]  H. Schwarz,et al.  Gas-phase characterization of the neutral and cationic Si2O2 molecules. A combined experimental and ab initio study , 1994 .

[18]  M. Ystenes.  Scaled quantum mechanical (SQM) vibrational analysis of monomeric silicon dioxide and its dimer 2,4-dioxo cyclodisiloxane Si2O4 , 1994 .

[19]  Nishikawa,et al.  Decay kinetics of the 4.4-eV photoluminescence associated with the two states of oxygen-deficient-type defect in amorphous SiO2. , 1994, Physical review letters.

[20]  A combined density functional theoretical and photoelectron spectroscopic study of Ge2O2 , 1995 .

[21]  L. Cederbaum,et al.  A new class of free stable doubly negative systems: First investigations on the SimO2−n series , 1995 .

[22]  V. Sulimov,et al.  Cluster modeling of the neutral oxygen vacancy in pure silicon dioxide , 1995 .

[23]  Lai‐Sheng Wang,et al.  Photoelectron spectroscopy of size‐selected transition metal clusters: Fe−n, n=3–24 , 1995 .

[24]  Lai‐Sheng Wang,et al.  Si3O4-: vibrationally resolved photoelectron spectrum and ab initio calculations , 1995 .

[25]  R. Elliott.  Evidence for rings in the dynamics of tetrahedral glasses , 1995 .

[26]  Lai‐Sheng Wang,et al.  A Photoelectron Spectroscopic Study of Small Silicon Oxide Clusters: SiO2, Si2O3, and Si2O4 , 1996 .

[27]  F. Stillinger,et al.  Structures and Energies of SiO 2 Clusters , 1996 .

[28]  L. Cederbaum,et al.  A new class of free stable doubly negative systems: Three Si2O2−5 isomers and their interconversion , 1996 .

[29]  P. Roy,et al.  Vibrational spectrum and structure of silicon trioxide SiO3: A matrix isolation infrared and density functional theory study , 1996 .