Abstract.
Ab initio multireference configuration interaction calculations for adiabatic potential curves, nonadiabatic couplings 〈φ i (R,r)|d/dR|φ j (R,r)〉 and 〈φ i (R,r)|d2/dR 2|φ j (R,r)〉, and nuclear kinetic energy corrections 〈dφ i (R,r)/dR|dφ i (R,r)/dR〉 for the (3sσ) B and (3pσ) C1Σ+ Rydberg states of the CO molecule have been carried out. The energy positions and predissociation linewidths for the observed vibrational levels of these two states have been determined in a rigorous adiabatic representation by the complex scaling method employing a basis of complex scaled harmonic vibrational functions in conjunction with the Gauss-Hermite quadrature method to evaluate the complex Hamiltonian matrix elements. The present treatment correctly reproduces the observed trends in energies and line broadening for vibrational levels of the B1Σ+ state and represents an improvement over the previous treatment in literature. The errors in the determined spacings of the v = 0–4 vibrational levels of the C1Σ+ state are less than 2% compared with measured data. The predissociation linewidths for the v=3,4 levels of the C1Σ+ state are found to be 4.9 and 8.9 cm−1, respectively, in good agreement with the observed values.
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Received: 23 March 1998 / Accepted: 27 July 1998 / Published online: 9 October 1998
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Li, Y., Buenker, R. & Hirsch, G. Theoretical treatment of predissociation of the CO (3sσ) B and (3pσ) C1Σ+ Rydberg states based on a rigorous adiabatic representation. Theor Chem Acc 100, 112–116 (1998). https://doi.org/10.1007/s002140050371
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DOI: https://doi.org/10.1007/s002140050371