Elsevier

Chemical Physics

Volume 181, Issues 1–2, 15 March 1994, Pages 217-245
Chemical Physics

Predissociation rates in carbon monoxide: dependence on rotational state, parity and isotope

https://doi.org/10.1016/0301-0104(94)85026-7Get rights and content

Abstract

A high-resolution spectroscopic study of carbon monoxide has been performed using a narrow-band and tunable extreme-ultraviolet laser source in the wavelength range 91–97 nm. For three isotopes 12C16, 13C16O and 13C18O the (4pπ)L 1Π, ν=0, (4pσ)K 1Σ+, ν=0 and (3sσ)W 1Π, ν=0 states were investigated. The 1Π, ν=2, (3sσ)W 1Π, ν=2 and (3dπ)L′ 1Π, ν=1 states were studied for 12C16 and 13C16O. The 1Π, ν=0 state at 109564.58 cm−1, the (6pσ) 1Σ+, ν=0 state at 109173.68 cm−1, the (5pσ) 1Σ+, ν=0 state at 107174.44 cm−1, and the (4dσ) 1Σ+, ν=0 state at 105676.30 cm−1 were excited only for the main isotope 16C16O. Previously unknwon states are found at 107365.87 cm−1 (1Σ+) for 12C16O and at 103203.07 cm−1 (1Π) for 13C18O. Indirect evidence is found for a perturber state at 107708±2 cm−2 cm−1 for 12C16O, while spectroscopic information on the E1Π, ν=5 state of 13C18O is deduced from a deperturbation analysis. A rotational-state and isotope-dependent predissociation rate is found for almost all states. A parity dependence is observed for the (4pπ)L 1Π, ν=0 and (3sσ)W 1Π, ν=0 states, where the predissociation rate of the Πe component varies proportional to J(J+1). This effect is attributed a coupling with the repulsive part of the D′ 1Σ+ state. Several examples of accidental predissociations have been found, particularly in the (4dσ) 1Σ+, ν=0 state.

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