A study of the structure and bonding of small aluminum oxide clusters by photoelectron spectroscopy: AlxOy- (x=1–2, y=1–5)
Abstract
The structure and bonding of aluminum oxide clusters, AlxOy (x=1–2, y=1–5), are studied with anion photoelectron spectroscopy (PES) and are compared with preliminary ab initio calculations. The spectra were obtained at four detachment photon energies: 2.33, 3.49, 4.66, and 6.42 eV. The 6.42 eV spectrum for AlO– reveals the X2Σ+ ground state and two excited states of AlO. The 6.42 eV spectrum for AlO2– also shows three states for AlO2: X2Πg ground state and the A2Πu and B2Σ+g excited states. The spectra for Al2Oy– clusters show vibrationally resolved ground states which come from Al sp-type orbitals and also high binding energy excited states, which are mainly of oxygen 2p character. Al2O2, which has a D2h rhombus structure, has an electron affinity (EA) of 1.88 eV and its singlet–triplet excitation energy is measured to be 0.49 eV. Much higher EAs are measured for the larger Al2Oy clusters. The PES spectra of Al2O–3, Al2O–4, and Al2O–5 show very similar electronic and vibrational structure. Furthermore, the ground state vibrational frequencies of these three molecules are also similar. Here these observations lead us to suggest that these molecules all have a rhombuslike structure, similar to Al2O2, with the oxygen atoms sequentially attaching to themore »
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Washington State Univ., Richland, WA (United States)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Richland, WA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 436404
- Grant/Contract Number:
- AC06-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 106; Journal Issue: 4; Other Information: PBD: Jan 1997; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 40 CHEMISTRY; ALUMINIUM OXIDES; CHEMICAL BONDS; CRYSTAL STRUCTURE; PHOTOELECTRON SPECTROSCOPY; ALUMINIUM COMPOUNDS; EXCITED STATES; GROUND STATES; AFFINITY; ANIONS; VIBRATIONAL STATES; MOLECULAR CLUSTERS; ELECTRONIC STRUCTURE; SOLID CLUSTERS; BONDING; MOLECULAR STRUCTURE; EV RANGE 01-10; ab initio calculations
Citation Formats
Desai, Sunil R., Wu, Hongbin, Rohlfing, Celeste M., and Wang, Lai -Sheng. A study of the structure and bonding of small aluminum oxide clusters by photoelectron spectroscopy: AlxOy- (x=1–2, y=1–5). United States: N. p., 1998.
Web. doi:10.1063/1.474085.
Desai, Sunil R., Wu, Hongbin, Rohlfing, Celeste M., & Wang, Lai -Sheng. A study of the structure and bonding of small aluminum oxide clusters by photoelectron spectroscopy: AlxOy- (x=1–2, y=1–5). United States. https://doi.org/10.1063/1.474085
Desai, Sunil R., Wu, Hongbin, Rohlfing, Celeste M., and Wang, Lai -Sheng. Thu .
"A study of the structure and bonding of small aluminum oxide clusters by photoelectron spectroscopy: AlxOy- (x=1–2, y=1–5)". United States. https://doi.org/10.1063/1.474085. https://www.osti.gov/servlets/purl/436404.
@article{osti_436404,
title = {A study of the structure and bonding of small aluminum oxide clusters by photoelectron spectroscopy: AlxOy- (x=1–2, y=1–5)},
author = {Desai, Sunil R. and Wu, Hongbin and Rohlfing, Celeste M. and Wang, Lai -Sheng},
abstractNote = {The structure and bonding of aluminum oxide clusters, AlxOy (x=1–2, y=1–5), are studied with anion photoelectron spectroscopy (PES) and are compared with preliminary ab initio calculations. The spectra were obtained at four detachment photon energies: 2.33, 3.49, 4.66, and 6.42 eV. The 6.42 eV spectrum for AlO– reveals the X2Σ+ ground state and two excited states of AlO. The 6.42 eV spectrum for AlO2– also shows three states for AlO2: X2Πg ground state and the A2Πu and B2Σ+g excited states. The spectra for Al2Oy– clusters show vibrationally resolved ground states which come from Al sp-type orbitals and also high binding energy excited states, which are mainly of oxygen 2p character. Al2O2, which has a D2h rhombus structure, has an electron affinity (EA) of 1.88 eV and its singlet–triplet excitation energy is measured to be 0.49 eV. Much higher EAs are measured for the larger Al2Oy clusters. The PES spectra of Al2O–3, Al2O–4, and Al2O–5 show very similar electronic and vibrational structure. Furthermore, the ground state vibrational frequencies of these three molecules are also similar. Here these observations lead us to suggest that these molecules all have a rhombuslike structure, similar to Al2O2, with the oxygen atoms sequentially attaching to the terminal aluminum atoms. The spectra are consistent with an ionic bonding view of these clusters and the vibrational frequencies are in good agreement with the theoretical results. Significant information about the structure and bonding of these small aluminum oxide clusters is obtained and discussed.},
doi = {10.1063/1.474085},
journal = {Journal of Chemical Physics},
number = 4,
volume = 106,
place = {United States},
year = {1998},
month = {6}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Fluorescence excitation and resolved emission spectra of supersonically cooled Al 2 O
journal, July 1991
- Cai, Mingfang; Carter, Christopher C.; Miller, Terry A.
- The Journal of Chemical Physics, Vol. 95, Issue 1
Infrared Spectrum and Structure of Gaseous Al 2 O
journal, July 1964
- Linevsky, Milton J.; White, David; Mann, D. E.
- The Journal of Chemical Physics, Vol. 41, Issue 2
Photodetachment spectroscopy of cold aluminum cluster anions
journal, April 1988
- Ganteför, G.; Meiwes-Broer, K. H.; Lutz, H. O.
- Physical Review A, Vol. 37, Issue 7
Electronic structure and molecular topology of boron and aluminum suboxides
journal, January 1981
- Dekock, Roger L.; Barbachyn, Michael R.
- Journal of Inorganic and Nuclear Chemistry, Vol. 43, Issue 11
Band strengths for electric dipole transitions from ab initio computation: Lio (X 2Π −X 2Π), (A 2Σ+−A 2Σ+), (X 2Π − A 2Σ+); AlO (X 2Σ+−X 2Σ+), (A 2Π −A 2Π), (X 2Σ+−A 2Π), (B 2Σ+−B 2Σ+), (X 2Σ+−B 2Σ+)
journal, May 1973
- Yoshimine, M.; McLean, A. D.; Liu, B.
- The Journal of Chemical Physics, Vol. 58, Issue 10
Magnetic time‐of‐flight photoelectron spectrometer for mass‐selected negative cluster ions
journal, November 1987
- Cheshnovsky, O.; Yang, S. H.; Pettiette, C. L.
- Review of Scientific Instruments, Vol. 58, Issue 11
Dissociation energies of the molecules AlO and Al2O
journal, May 1973
- Hildenbrand, D. L.
- Chemical Physics Letters, Vol. 20, Issue 1
Si3O4-: vibrationally resolved photoelectron spectrum and ab initio calculations
journal, May 1995
- Fan, Jiawen; Nicholas, John. B.; Price, John M.
- Journal of the American Chemical Society, Vol. 117, Issue 19
Matrix reactions of molecular oxygen and ozone with aluminum atoms
journal, May 1983
- Sonchik, Susan M.; Andrews, Lester; Carlson, K. Douglas
- The Journal of Physical Chemistry, Vol. 87, Issue 11
Negative ion photoelectron spectroscopy of chromium dimer
journal, January 1993
- Casey, Sean M.; Leopold, Doreen G.
- The Journal of Physical Chemistry, Vol. 97, Issue 4
Reactions of pulsed-laser evaporated aluminum atoms with oxygen: infrared spectra of the reaction products in solid argon
journal, December 1992
- Andrews, Lester; Burkholder, Thomas R.; Yustein, Jason T.
- The Journal of Physical Chemistry, Vol. 96, Issue 25
Analysis of an anomalous vibrational dependence of the spin-rotation constants for A1O (X 2Σ+)
journal, September 1994
- Ita, Haruhiko; Goto, Masahiro
- Chemical Physics Letters, Vol. 227, Issue 3
Theoretical investigations of AlO2
journal, January 1992
- Nemukhin, A. V.; Almlöf, J.
- Journal of Molecular Structure: THEOCHEM, Vol. 253
Ground state spectroscopic and thermodynamic properties of AlO − , SiN − , CP − , BS − , BO − , and CN − from Mo/ller–Plesset perturbation theory
journal, June 1989
- Peterson, Kirk A.; Woods, R. Claude
- The Journal of Chemical Physics, Vol. 90, Issue 12
Infrared spectra of the products of reaction of aluminium, gallium, indium, and thallium with oxygen in an argon matrix. Estimation of the fundamentals, v3, in cyclic superoxides of group iii metals
journal, April 1982
- Serebrennikov, L. V.; Osin, S. B.; Maltsev, A. A.
- Journal of Molecular Structure, Vol. 81, Issue 1-2
Characterization of cluster ions produced by the sputtering or direct laser vaporization of group 13 metal (Al, Ga, and In) oxides
journal, February 1991
- King, Fred L.; Dunlap, Brett I.; Parent, Denise C.
- The Journal of Chemical Physics, Vol. 94, Issue 4
The reactions of mass selected aluminum cluster ions, Al + n ( n =4–25), with oxygen
journal, November 1986
- Jarrold, Martin F.; Bower, J. Eric
- The Journal of Chemical Physics, Vol. 85, Issue 9
Aluminum clusters: Magnetic properties
journal, April 1986
- Cox, D. M.; Trevor, D. J.; Whetten, R. L.
- The Journal of Chemical Physics, Vol. 84, Issue 8
Transition-State Spectroscopy of Cyclooctatetraene
journal, June 1996
- Wenthold, P. G.; Hrovat, D. A.; Borden, W. T.
- Science, Vol. 272, Issue 5267
Structure and relative stability of the aluminate anion studied by quantum chemical methods
journal, March 1994
- Nianyi, Chen; Honglin, Liu
- Journal of Molecular Structure: THEOCHEM, Vol. 305
Spectroscopic studies of AlO in argon matrices
journal, January 1985
- Bares, S. J.; Haak, M.; Nibler, J. W.
- The Journal of Chemical Physics, Vol. 82, Issue 2
Ab initio dipole moment functions for the X 2 Σ + and B 2 Σ + states of AlO
journal, December 1982
- Lengsfield, B. H.; Liu, B.
- The Journal of Chemical Physics, Vol. 77, Issue 12
Size-dependent barriers for reaction of aluminum cluster ions with oxygen
journal, May 1987
- Ruatta, Stephen A.; Hanley, Luke; Aanderson, Scott L.
- Chemical Physics Letters, Vol. 137, Issue 1
Spectroscopic properties and potential energy curves of some low-lying electronic states of AlO, AlO + , LaO, and LaO + : An ab initio CASSCF study : LOW-LYING ELECTRONIC STATES OF AlO, AlO
journal, December 1994
- Márquez, Antonio; Capitán, Maria José; Odriozola, José Antonio
- International Journal of Quantum Chemistry, Vol. 52, Issue 6
Aluminum Oxide Sputtering: A New Approach to Understanding the Sputtering Process for Binary Targets
book, June 1976
- Finn, Patricia A.; Gruen, Dieter M.; Page, Dennis L.
- Radiation Effects on Solid Surfaces, p. 30-64
Electronic Structure of Small Titanium Clusters: Emergence and Evolution of the Band
journal, January 1996
- Wu, Hongbin; Desai, Sunil R.; Wang, Lai-Sheng
- Physical Review Letters, Vol. 76, Issue 2
Reactivities of spin-orbit states in () + (X3Σg−) → Σ) + (. A fluorescence imaging study
journal, June 1995
- Chen, Kuo-mei; Sung, Chun-hwa; Chang, Jia-lin
- Chemical Physics Letters, Vol. 240, Issue 1-3
Reinvestigation of the symmetric stretching mode of matrix-isolated dialuminum monoxide
journal, January 1974
- Lynch, Denis A.; Zehe, Michael J.; Carlson, K. Douglas
- The Journal of Physical Chemistry, Vol. 78, Issue 3
Photoelectron spectroscopy of size‐selected transition metal clusters: Fe − n , n =3–24
journal, June 1995
- Wang, Lai‐Sheng; Cheng, Han‐Song; Fan, Jiawen
- The Journal of Chemical Physics, Vol. 102, Issue 24
Theoretical investigations of the isomerization of Al2O2
journal, April 1993
- Zaitsevskii, A. V.; Chertihin, G. V.; Serebrennikov, L. V.
- Journal of Molecular Structure: THEOCHEM, Vol. 280, Issue 2-3
Infrared spectra of the aluminum family suboxides. Comments
journal, November 1973
- Marino, Charles P.; White, David
- The Journal of Physical Chemistry, Vol. 77, Issue 24
Structures of the aluminum oxides studied by ab initio methods with natural bond orbital analysis
journal, September 1992
- Nemukhin, A. V.; Weinhold, F.
- The Journal of Chemical Physics, Vol. 97, Issue 5
Evolution of the Electronic Structure of Small Vanadium Clusters from Molecular to Bulklike
journal, September 1996
- Wu, Hongbin; Desai, Sunil R.; Wang, Lai-Sheng
- Physical Review Letters, Vol. 77, Issue 12
Electronic and vibrational structure of transition metal trimers: Photoelectron spectra of Ni − 3 , Pd − 3 , and Pt − 3
journal, October 1988
- Ervin, Kent M.; Ho, Joe; Lineberger, W. C.
- The Journal of Chemical Physics, Vol. 89, Issue 8
On the structure of the A1O2 dimer, A12O4
journal, December 1994
- Nemukhin, A. V.
- Journal of Molecular Structure: THEOCHEM, Vol. 315
Electronic transition moment of the (Σ−Σ) emission. Analysis of the R dependence of the Al2+O2− character in the Σ state
journal, June 1995
- Sato, Noriko; Ito, Haruhiko; Kuchitsu, Kozo
- Chemical Physics Letters, Vol. 240, Issue 1-3
New experimental setup for photoelectron spectroscopy on cluster anions
journal, December 1992
- Cha, Chia‐Yen; Ganteför, G.; Eberhardt, W.
- Review of Scientific Instruments, Vol. 63, Issue 12
Large ion volume time‐of‐flight mass spectrometer with position‐ and velocity‐sensitive detection capabilities for cluster beams
journal, March 1991
- de Heer, Walt A.; Milani, Paolo
- Review of Scientific Instruments, Vol. 62, Issue 3
A detailed study of the reactions between size selected aluminum cluster ions, Al + n ( n =3–26), and oxygen
journal, November 1987
- Jarrold, Martin F.; Bower, J. Eric
- The Journal of Chemical Physics, Vol. 87, Issue 10
The C2Π − X2Σ+ (0, 0) Band in AlO
journal, January 1994
- Towle, J. P.; James, A. M.; Bourne, O. L.
- Journal of Molecular Spectroscopy, Vol. 163, Issue 1
Microwave spectra of the AlO (X 2Σ+) radical in the v= 1 and 2 states
journal, September 1994
- Goto, Masahiro; Takano, Shuro; Yamamoto, Satoshi
- Chemical Physics Letters, Vol. 227, Issue 3
An ab-Initio Study of the Structures and Harmonic Vibrational Frequencies of M2O2 (M = Al, Ga, In, Tl)
journal, October 1995
- Archibong, Edet F.; Sullivan, Richard
- The Journal of Physical Chemistry, Vol. 99, Issue 43
Magnetic field paralleliser for 2π electron-spectrometer and electron-image magnifier
journal, April 1983
- Kruit, P.; Read, F. H.
- Journal of Physics E: Scientific Instruments, Vol. 16, Issue 4
Infrared spectra of the aluminum family suboxides
journal, June 1971
- Carlson, K. Douglas; Makowiecki, Daniel M.; Lynch, Denis A.
- The Journal of Physical Chemistry, Vol. 75, Issue 13
Photoelectron spectra of the alkali metal cluster anions: Na − n =2–5 , K − n =2–7 , Rb − n =2–3 , and Cs − n =2–3
journal, September 1989
- McHugh, K. M.; Eaton, J. G.; Lee, G. H.
- The Journal of Chemical Physics, Vol. 91, Issue 6
The microwave spectrum of the AlO radical
journal, February 1990
- Yamada, Chikashi; Cohen, Edward A.; Fujitake, Masaharu
- The Journal of Chemical Physics, Vol. 92, Issue 4
Doublet instability and the molecular structure of AlO2
journal, December 1988
- Rubio, J.; Ricart, J. M.; Illas, F.
- Journal of Computational Chemistry, Vol. 9, Issue 8
Electronic structure of small copper oxide clusters: From O to
journal, March 1996
- Wang, Lai-Sheng; Wu, Hongbin; Desai, Sunil R.
- Physical Review B, Vol. 53, Issue 12
Detection of AlO molecules produced by KrF laser‐ablated Al atoms in oxygen gas and plasma environments
journal, September 1995
- Ching, C. H.; Gilgenbach, R. M.; Lash, J. S.
- Journal of Applied Physics, Vol. 78, Issue 5
Study of the low‐lying electronic states of Si 2 and Si − 2 using negative ion photodetachment techniques
journal, August 1991
- Kitsopoulos, T. N.; Chick, C. J.; Zhao, Y.
- The Journal of Chemical Physics, Vol. 95, Issue 3
Molecular structure and vibrational frequencies of AlxOy (x=1,2; y⩽3) derived from ab initio calculations
journal, March 1988
- Masip, J.; Clotet, A.; Ricart, J. M.
- Chemical Physics Letters, Vol. 144, Issue 4
Ab initio study on the Al2O, Al2O2, Si2O2 and AlSiO2 oxides and on the LiAlO2 and NaAlO2 molecules
journal, January 1992
- Bencivenni, L.; Pelino, M.; Ramondo, F.
- Journal of Molecular Structure: THEOCHEM, Vol. 253
ESR and Optical Spectroscopy of the AlO Molecule at 4°K; Observation of an Al Complex and Its Interaction with Krypton
journal, November 1971
- Knight, L. B.; Weltner, W.
- The Journal of Chemical Physics, Vol. 55, Issue 10
Two isomers of CuO 2 : The Cu(O 2 ) complex and the copper dioxide
journal, September 1995
- Wu, Hongbin; Desai, Sunil R.; Wang, Lai‐Sheng
- The Journal of Chemical Physics, Vol. 103, Issue 10
Bending frequency of gaseous aluminum oxide
journal, June 1970
- Suelson, A.
- The Journal of Physical Chemistry, Vol. 74, Issue 12
The AlO + O2 Reaction System over a Wide Temperature Range
journal, August 1995
- Belyung, David P.; Fontijn, Arthur
- The Journal of Physical Chemistry, Vol. 99, Issue 32
Thermodynamic Study of Al 2 O 3 Using a Mass Spectrometer
journal, May 1960
- Drowart, J.; DeMaria, G.; Burns, R. P.
- The Journal of Chemical Physics, Vol. 32, Issue 5
A combined density functional theoretical and photoelectron spectroscopic study of Ge 2 O 2
journal, May 1995
- Nicholas, John B.; Fan, Jiawen; Wu, Hongbin
- The Journal of Chemical Physics, Vol. 102, Issue 20
Mass distributions of binary aluminium cluster anions AlnXm− (X = O, S, P, As, C)
journal, February 1995
- Liu, Zhao-Yang; Wang, Chun-Ru; Huang, Rong-Bin
- International Journal of Mass Spectrometry and Ion Processes, Vol. 141, Issue 3
Chemiluminescence and reactivity of aluminum monoxide (AlO) in the excited B(2Σ+) state
journal, October 1995
- Bescós, B.; Morley, G.; González Ureña, A.
- Chemical Physics Letters, Vol. 244, Issue 5-6
Works referencing / citing this record:
Role of implants surface modification in osseointegration: A systematic review
journal, November 2019
- Liu, Yu; Rath, Björn; Tingart, Markus
- Journal of Biomedical Materials Research Part A, Vol. 108, Issue 3
Density functional study of neutral and anionic AlOn and ScOn with high oxygen content
journal, July 2011
- Gutsev, G. L.; Weatherford, C. A.; Pradhan, K.
- Journal of Computational Chemistry, Vol. 32, Issue 14
Biocompatibility of alumina-based biomaterials-A review: RAHMATI and MOZAFARI
journal, September 2018
- Rahmati, Maryam; Mozafari, Masoud
- Journal of Cellular Physiology, Vol. 234, Issue 4
The Limits of the Post‐Growth Optimization of AlN Thin Films Grown on Si(111) via Magnetron Sputtering
journal, December 2019
- Solonenko, Dmytro; Schmidt, Constance; Stoeckel, Chris
- physica status solidi (b), Vol. 257, Issue 5
Structure characterization of metal oxide clusters by vibrational spectroscopy: possibilities and prospects
journal, January 2012
- Asmis, Knut R.
- Physical Chemistry Chemical Physics, Vol. 14, Issue 26
Investigation of plasma electrolytic oxidation on valve metals by means of molecular spectroscopy – a review
journal, January 2014
- Stojadinović, Stevan; Vasilić, Rastko; Perić, Miljenko
- RSC Adv., Vol. 4, Issue 49
A photoelectron spectroscopy and quantum chemical study on ternary Al–B–O clusters: Al n BO 2 − and Al n BO 2 ( n = 2, 3)
journal, January 2018
- Ou, Ting; Feng, Yuan; Tian, Wen-Juan
- Physical Chemistry Chemical Physics, Vol. 20, Issue 7
Photoelectron spectra of Al 2 O 2 − and Al 3 O 3 − via slow electron velocity-map imaging
journal, January 2019
- DeVine, Jessalyn A.; Babin, Mark C.; Neumark, Daniel M.
- Faraday Discussions, Vol. 217
Interplay between pulsation, mass loss, and third dredge-up: More about Miras with and without technetium
journal, February 2019
- Uttenthaler, S.; McDonald, I.; Bernhard, K.
- Astronomy & Astrophysics, Vol. 622
A study of nickel monoxide (NiO), nickel dioxide (ONiO), and Ni(O2) complex by anion photoelectron spectroscopy
journal, July 1997
- Wu, Hongbin; Wang, Lai-Sheng
- The Journal of Chemical Physics, Vol. 107, Issue 1
A photoelectron spectroscopic study of monovanadium oxide anions (VOx−, x=1–4)
journal, April 1998
- Wu, Hongbin; Wang, Lai-Sheng
- The Journal of Chemical Physics, Vol. 108, Issue 13
Performance of density functionals for the structure and energetics of (M–O) 0,± (M=Al, Si, Sc–Zn)
journal, December 2018
- Sampathkumar, Suresh; Paranthaman, Selvarengan
- Molecular Simulation, Vol. 45, Issue 6
Combined experimental and theoretical study of small aluminum oxygen clusters
journal, October 2007
- Neukermans, S.; Veldeman, N.; Janssens, E.
- The European Physical Journal D, Vol. 45, Issue 2
Coagulation of the Ionized Combustion Products in a Dust Flame of Aluminum Particles
journal, June 2019
- Poletaev, N. I.; Khlebnikova, M. Y.
- Journal of Chemistry, Vol. 2019
Role of implants surface modification in osseointegration : A systematic review
text, January 2020
- Liu, Yu; Rath, Björn; Tingart, Markus
- RWTH Aachen University
Interplay between pulsation, mass loss, and third dredge-up: More about Miras with and without technetium
text, January 2018
- Uttenthaler, Stefan; McDonald, Iain; Bernhard, Klaus
- arXiv
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