Configuration interaction studies on low-lying states of O2

Barry J. Moss; William A. Goddard

doi:10.1063/1.431791

Configuration interaction studies on low-lying states of O₂

Barry J. Moss
, William A. Goddard

California Institute of Technology

Research output: Contribution to journal › Article › peer-review

Abstract

We report configuration interaction calculations as a function of internuclear distance for the nine states of O₂ corresponding to the (3σ_g)² (1π_u)² (1π_g)² and (3σ_g)² (1π_u)³ (1π_g)³ configurations, that is, X³Σ_g^-, a ¹Δ _g, b ¹Σ_g⁺, c ¹Σ_g⁺, C ³Δ_u, A ³Σ_u⁺, B ³Σ _u^-, ¹Δ_u, ¹Σ _u⁺. By using the generalized valence bond (GVB) orbitals of the X ³Σ_g^- state, we obtain good quality GVB-CI wavefunctions with only a moderate number of configurations (72 to 98 spatial configurations) despite the use of a large basis set (double-zeta plus d polarization functions). The calculated D_e for the X ₃³Σ_g^- state is 4.88 eV, 93% of the experimental value. The calculated adiabatic excitation energies are on the average about 0.1 eV from the experimental values.

Original language	English
Pages (from-to)	3523-3531
Number of pages	9
Journal	Journal of Chemical Physics
Volume	63
Issue number	8
DOIs	https://doi.org/10.1063/1.431791
Publication status	Published - 1 Jan 1975
Externally published	Yes

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title = "Configuration interaction studies on low-lying states of O2",

abstract = "We report configuration interaction calculations as a function of internuclear distance for the nine states of O2 corresponding to the (3σg)2 (1πu)2 (1πg)2 and (3σg)2 (1πu)3 (1πg)3 configurations, that is, X3Σg-, a 1Δ g, b 1Σg+, c 1Σg+, C 3Δu, A 3Σu+, B 3Σ u-, 1Δu, 1Σ u+. By using the generalized valence bond (GVB) orbitals of the X 3Σg- state, we obtain good quality GVB-CI wavefunctions with only a moderate number of configurations (72 to 98 spatial configurations) despite the use of a large basis set (double-zeta plus d polarization functions). The calculated De for the X 33Σg- state is 4.88 eV, 93\% of the experimental value. The calculated adiabatic excitation energies are on the average about 0.1 eV from the experimental values.",

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T1 - Configuration interaction studies on low-lying states of O2

AU - Moss, Barry J.

AU - Goddard, William A.

PY - 1975/1/1

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N2 - We report configuration interaction calculations as a function of internuclear distance for the nine states of O2 corresponding to the (3σg)2 (1πu)2 (1πg)2 and (3σg)2 (1πu)3 (1πg)3 configurations, that is, X3Σg-, a 1Δ g, b 1Σg+, c 1Σg+, C 3Δu, A 3Σu+, B 3Σ u-, 1Δu, 1Σ u+. By using the generalized valence bond (GVB) orbitals of the X 3Σg- state, we obtain good quality GVB-CI wavefunctions with only a moderate number of configurations (72 to 98 spatial configurations) despite the use of a large basis set (double-zeta plus d polarization functions). The calculated De for the X 33Σg- state is 4.88 eV, 93% of the experimental value. The calculated adiabatic excitation energies are on the average about 0.1 eV from the experimental values.

AB - We report configuration interaction calculations as a function of internuclear distance for the nine states of O2 corresponding to the (3σg)2 (1πu)2 (1πg)2 and (3σg)2 (1πu)3 (1πg)3 configurations, that is, X3Σg-, a 1Δ g, b 1Σg+, c 1Σg+, C 3Δu, A 3Σu+, B 3Σ u-, 1Δu, 1Σ u+. By using the generalized valence bond (GVB) orbitals of the X 3Σg- state, we obtain good quality GVB-CI wavefunctions with only a moderate number of configurations (72 to 98 spatial configurations) despite the use of a large basis set (double-zeta plus d polarization functions). The calculated De for the X 33Σg- state is 4.88 eV, 93% of the experimental value. The calculated adiabatic excitation energies are on the average about 0.1 eV from the experimental values.

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DO - 10.1063/1.431791

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SN - 0021-9606

VL - 63

SP - 3523

EP - 3531

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 8

ER -

Configuration interaction studies on low-lying states of O₂

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