ISSN:
1432-2234
Keywords:
Key words: Carbon monoxide
;
Predissociation
;
Rydberg states
;
Nonadiabatic coupling
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/s002140050371
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