Abstract
It is shown how a carefully devised quantum defect function can be used to unify direct dissociation of the lowest member of a Rydberg series, with predissociation of the higher vibronic states. Results, for a one-dimensional model, obtained by the techniques of multichannel quantum defect theory (MQDT) are compared with those of a simpler Fano golden rule approximation. A simplified model calculation for the ns1B1 series of H2O and D2O yields results in good accord with experiment, and a dramatic isotope effect is explained. A similar application to the elusive np1A2 series leads to the prediction of sharp rotational structure for the np1A2(000) bands with n≥4, despite the evidence of a very broad Franck–Condon profile for the dissociative 3p1A2 state. A band at 90 051 cm−1 in the 2+1 REMPI spectrum is tentatively assigned to the 4p member of this 1A2 series.
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