Theoretical study of the 2A22B2 separation of the alkali superoxides

Bauschlicher, Charles W.; Sodupe, Mariona; Partridge, Harry; Langhoff, Stephen R.

doi:10.1016/0009-2614(92)85757-2

Cited by 9 publications

(21 citation statements)

References 17 publications

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“…The data in Table for NaO 2 (X 2 A 2 ) follow the same trends as those in Table for LiO 2 (X 2 A 2 ), i.e., small Δ g xx of 82 ppm, large Δ g yy of 92 646 ppm (governed by the coupling with 1 2 B 2 ), and a medium Δ g zz component (7185 ppm) with two excited states dominating the SOS expansion. Lowering the vertical Δ E (1 2 B 2 ) value for NaO 2 by 0.072 eV after comparing with Bauschlicher's data, Δ g yy increases by about 21% (Table , footnote c ). The g yy shift of NaO 2 is about twice the value for LiO 2 , mainly because Δ E (NaO 2 ) ≈ (1/2) Δ E (LiO 2 ).…”

Section: Methodsmentioning

confidence: 85%

“…The small deformation of the π g components 1a 2 and 2b 2 is evident by a L value close to 1.0 (Table ). Since the energy difference is a critical parameter for evaluating Δ g , we have compared our calculated adiabatic T e (1 2 B 2 ) value with that reported in a more extensive treatment . Our CI value is too high by 0.056 eV.…”

Section: Methodsmentioning

confidence: 95%

“…The second-order Δ g values have also been calculated for the 1 2 B 2 state of LiO 2 , at the equilibrium geometry given in ref . The corresponding contributions (in ppm) to Δ g xx , Δ g yy , and Δ g zz are 8685, −61 454, and 59.…”

Section: Methodsmentioning

confidence: 99%

“…b At its equilibrium geometry (ref ), and using X 2 A 2 SCF MOs. c At its equilibrium geometry (ref ), and using 1 2 B 2 SCF MOs. d Two 2 A 1 states at the CI level, given as MRCI1 and MRCI2.…”

Section: Methodsmentioning

confidence: 99%

“…The separation Δ E between the lowest 2 Π and 2 Σ + states of the alkali oxides M−O and between the lowest 2 A 2 and 2 B 2 states of the superoxides MO 2 were determined theoretically. Both MO 2 states have C 2 v equilibrium geometries, with the R e and ω e values of the O 2 moiety being similar to those of O 2 - ; i.e., the superoxides have the structure M + O 2 - .…”

Section: Literature Reviewmentioning

confidence: 99%

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Electron-Spin Magnetic Moments (g Factors) of the Oxides LiO, NaO, and the Superoxides LiO₂, NaO₂. An ab Initio Study

Bruna

Grein

1999

J. Phys. Chem. A

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The electron-spin magnetic moments of the superoxides LiO 2 and NaO 2 , as parametrized by the g factors, are studied at the uncorrelated (ROHF) and correlated (MRCI) ab initio levels. The present method, which uses a perturbative approach complete to second order, is based on the Breit-Pauli Hamiltonian. In the standard C 2V notation for the MO 2 radicals, ∆g yy > ∆g zz . |∆g xx |, where ∆g aa ) g aag e . The perpendicular component ∆g xx , which is small and negative, is dictated by first-order terms (ground-state expectation values). The in-plane components ∆g yy and ∆g zz are large and positive. ∆g yy is governed by the second-order magnetic coupling between X 2 A 2 and 1 2 B 2 (electron excitation from the highest b 2 MO into the a 2 (π*) SOMO), and ∆g zz by the coupling with two 2 A 1 states (excitations from the two highest a 1 MOs into π*). The calculated data reproduce the experimental trends reasonable well. For the ground state X 2 A 2 , the MRCI results for ∆g xx , ∆g yy , ∆g zz (in ppm, with ppm ) 10 -6 ) are -373 (-350), 56 800 (56 250), 7273 (6600) for LiO 2 ; and -393 (150), 110 492 (108 600), 6868 (4600) for NaO 2 , with the experimental results given in parentheses (average from Ar and Kr matrices). For comparison purposes, the g shifts of the low-lying excited state 1 2 B 2 of LiO 2 and NaO 2 , as well as the magnetic coupling parameters for O 2 -, LiO, and NaO, are also reported.

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Section: Methodsmentioning

confidence: 85%

Section: Methodsmentioning

confidence: 95%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Literature Reviewmentioning

confidence: 99%

See 3 more Smart Citations