The low lying electronic states of O−3

Koch, Wolfram; Frenking, Gernot; Steffen, G.; Reinen, D.; Jansen, M.; Assenmacher, W.

doi:doi:10.1063/1.465371

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A direct algorithm for self‐consistent‐field linear response theory and application to C₆₀: Excitation energies, oscillator strengths, and frequency‐dependent polarizabilities

We present a direct self‐consistent‐field (SCF)‐type algorithm and its implementation for the computation of linear response properties: excitation energies, oscillator strengths, and frequency‐dependent polarizabilities within the time‐dependent SCF or random phase approximation. The treatment of singles configuration interaction for electronic excitations and Hartree–Fock instability criteria are covered as special cases. The algorithm is based on proven direct SCF methodology. This, together ...

Unified kernel function approach to two‐center integrations in quantum‐chemical calculations

We present a unified kernel function treatment of the two‐center integrals over atomic orbitals appearing in quantum chemical calculations on the basis of density functional theory. By using the Fourier transform method, we obtain analytical expressions for the kernel functions, from which actual integral values can be evaluated through twofold integration. As our only assumption is that the angular dependences of the atomic basis functions is given by spherical harmonics, our kernel functions a...

The energies of the three lowest lying excited states of the ozonide anion (1 ²B₂, 1 ²A₁, 1 ²A₂) at the optimized geometry of the X ²B₁ ground state are theoretically predicted at the MRCI‐SD level of theory using large atomic natural basis sets. The calculated vertical excitation energy T_v=2.85 eV for the 1 ²A₂←X ²B₁ transition, which has a large transition moment, is in good agreement with the experimental results for the isolated O₃⁻ anion in host matrices and solution between 2.69–2.81 eV. The state symmetry forbidden transition 1 ²B₂←X ²B₁ is calculated with T_v=2.26 eV. The excitation energy for the 1 ²A₁←X ²B₁ transition is theoretically predicted with T_v=2.28 eV and a very low transition moment. The theoretical results are also discussed in comparison with recently observed low lying absorption bands of O₃⁻.

KEYWORDS and PACS

Keywords

EXCITED STATES, ANIONS, OPTIMIZATION, GEOMETRY, GROUND STATES, EXCITATION, OZONE, MOLECULAR IONS, MATRIX ISOLATION, FORBIDDEN TRANSITIONS, EV RANGE 01−10

PACS

33.70.Ca

Oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
31.50.Df

Potential energy surfaces for excited electronic states