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PNO-CI and CEPA studies of electron correlation effects

II. Potential curves and dipole moment functions of the OH radical

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Abstract

Ab initio calculations of the potential curves of low laying electronic states of OH are performed on the basis of a variational configuration interaction wavefunction (PNO-CI) and the coupled electron pair approximation (CEPA).

The latter approach yields a ground state potential curve which deviates from the RKR curve by less than 200 cm−1 in the region from 0.7 to 1.6 Å. Calculated ground state constants are as follows (experimental values in parentheses): r e = 0.972 (0.971) Å, B e = 18.85 (18.87) cm−1, α e = 0.727 (0.714) cm−1, ω e = 3742 (3739) cm−1, ω e χ e = 85.3 (86.4) cm−1, μ0 = 1.686 (1.66) D, D e = 4.35 (4.63) eV,IP = 12.78 (13.36?) eV, El.Aff. = 1.51 (1.83) eV, v 00(2Π↔2Σ+) = 32690(32440) cm−1.

The correlation contributions to ionization, excitation and electron attachment are analyzed. On the basis of estimated CEPA-limits, which are in very good agreement with experiment for D e and electron affinity, an IP of 13.0eV is recommended. Dipole moment expectation values and some IR transition probabilities are calculated from the ground state dipole moment curves. The calculated crossing point of the 2Σ− curve with the repulsive 4Σ− state is not in agreement with the position deduced from intensity data.

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Authors and Affiliations

  1. Institut für Physikalische Chemie der Universität Mainz, Germany

    Wilfried Meyer

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  1. Wilfried Meyer
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Dedicated to Professor Hermann Hartmann on the occasion of his 60th birthday.

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Meyer, W. PNO-CI and CEPA studies of electron correlation effects. Theoret. Chim. Acta 35, 277–292 (1974). https://doi.org/10.1007/BF00548478

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