The sodium superoxide radical

2A2 and à 2B2 potential energy surfaces

David A. Horner, Wesley D. Allen, A. Császár, Henry F. Schaefer

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

The two lowest electronic states of NaO2 have been studied using ab initio methods, including RHF SCF, CISD, Davidson corrected CISD, UHF SCF, UMP2-UMP4, CASSCF, and CISD on CASSCF based natural orbitals, with basis sets ranging in quality from Na(11s7p/7s5p), O(9s5pld/5s3pld) to Na(13s10p2dlf/7s6p2dlf), O(11s7p2dlf/6s4p2dlf), i.e. from TZ+d to TZ2P+f+R. Total and relative energies, geometries, vibrational frequencies, and dipole moments of stationary points on the X̃2A2 and Ã2B2 surfaces have been determined. A C2v minimum is proposed for X̃2A2 NaO2 with re (OO)=1.335 and re(NaO)=2.10 Å. The analogous structure for the Ã2B2 state is predicted to have re(OO)=1.34 and re(NAO)=2.13 Å with an adiabatic excitation energy of Te=8.5 kcal mol-1. Linear, 2ΠNaOO, which correlates to the 2A2 and 2B2 minima via Cs transition states, is predicted to be a shallow minimum lying 17 kcal mol-1 above the X̃2A2 structure but with a barrier to rearrangement of less than 1 kcal mol-1. The dissociation energy of the ground state of NaO2 is deduced to be D0=38 kcal mol-1, a value substantially lower than recent experiment estimates.

Original languageEnglish
Pages (from-to)346-355
Number of pages10
JournalChemical Physics Letters
Volume186
Issue number4-5
DOIs
Publication statusPublished - Nov 15 1991

Fingerprint

Potential energy surfaces
Excitation energy
inorganic peroxides
Dipole moment
Electronic states
Vibrational spectra
Superoxides
Ground state
Sodium
potential energy
sodium
self consistent fields
Geometry
Experiments
energy
dipole moments
dissociation
orbitals
ground state
estimates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

The sodium superoxide radical : X̃2A2 and à 2B2 potential energy surfaces. / Horner, David A.; Allen, Wesley D.; Császár, A.; Schaefer, Henry F.

In: Chemical Physics Letters, Vol. 186, No. 4-5, 15.11.1991, p. 346-355.

Research output: Contribution to journalArticle

Horner, David A. ; Allen, Wesley D. ; Császár, A. ; Schaefer, Henry F. / The sodium superoxide radical : X̃2A2 and à 2B2 potential energy surfaces. In: Chemical Physics Letters. 1991 ; Vol. 186, No. 4-5. pp. 346-355.
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abstract = "The two lowest electronic states of NaO2 have been studied using ab initio methods, including RHF SCF, CISD, Davidson corrected CISD, UHF SCF, UMP2-UMP4, CASSCF, and CISD on CASSCF based natural orbitals, with basis sets ranging in quality from Na(11s7p/7s5p), O(9s5pld/5s3pld) to Na(13s10p2dlf/7s6p2dlf), O(11s7p2dlf/6s4p2dlf), i.e. from TZ+d to TZ2P+f+R. Total and relative energies, geometries, vibrational frequencies, and dipole moments of stationary points on the X̃2A2 and {\~A}2B2 surfaces have been determined. A C2v minimum is proposed for X̃2A2 NaO2 with re (OO)=1.335 and re(NaO)=2.10 {\AA}. The analogous structure for the {\~A}2B2 state is predicted to have re(OO)=1.34 and re(NAO)=2.13 {\AA} with an adiabatic excitation energy of Te=8.5 kcal mol-1. Linear, 2ΠNaOO, which correlates to the 2A2 and 2B2 minima via Cs transition states, is predicted to be a shallow minimum lying 17 kcal mol-1 above the X̃2A2 structure but with a barrier to rearrangement of less than 1 kcal mol-1. The dissociation energy of the ground state of NaO2 is deduced to be D0=38 kcal mol-1, a value substantially lower than recent experiment estimates.",
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