Anomalous Q branch intensity in the 2+1 rempi spectrum of the 1Π-1Σ+ transition in highly rotationally excited CO photofragments from OCS photodissociation at 215 nm
Gunthardt, Carolyn E.
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https://hdl.handle.net/2142/100538
Description
Title
Anomalous Q branch intensity in the 2+1 rempi spectrum of the 1Π-1Σ+ transition in highly rotationally excited CO photofragments from OCS photodissociation at 215 nm
Author(s)
Gunthardt, Carolyn E.
Contributor(s)
North, Simon
Hall, Gregory
Wallace, Colin J.
Issue Date
2018-06-20
Keyword(s)
Small molecules
Abstract
Nascent CO (X 1Σ +) photoproducts formed in the dissociation of OCS at 215 nm were probed using 2+1 resonance enhanced multiphoton ionization (REMPI) through the E 1Π state. This photodissociation produces a highly rotationally excited CO distribution, with fragment rotational levels ranging from J=48 to J=77. The resulting REMPI spectrum contains a prominent Q branch, despite negligible line strength factors for high J, two-photon, Π-Σ, Q branch transitions. The presence of a Q branch in the spectrum is explained by intensity borrowing from the nearby C 1Σ + state, as coupling between the C and E states is well documented, and two photon, Σ-Σ, Q branch transitions are intense for high J states. The observed relative intensities of the Q and S branch lines are well described by extrapolation to high J of the J-dependent mixing of C and E states inferred from the E state lambda doublet splittings at lower J. Improved De and Df constants have been derived through the incorporation of this high J data.
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