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We observe photoabsorption of the W(1) ← X(0) band in five carbon monoxide isotopologues with a vacuum-ultraviolet Fourier-transform spectrometer and a synchrotron radiation source. We deduce transition energies, integrated cross sections, and natural linewidths of the observed rotational transitions and find a perturbation affecting these. Following a deperturbation analysis of all five isotopologues, the perturbing state is assigned to the v = 0 level of a previously unobserved (1)Π state predicted by ab initio calculations to occur with the correct symmetry and equilibrium internuclear distance. We label this new state E″ (1)Π. Both of the interacting levels W(1) and E″(0) are predissociated, leading to dramatic interference effects in their corresponding linewidths.

We present high-resolution absorption spectral measurements of the A(1)Π-X(1)Σ(+) band system of (13)C(16)O. These were recorded with the VUV Fourier transform spectrometer (VUV-FTS) installed on the DESIRS beamline at the SOLEIL synchrotron. This work includes revised term values that extend to higher J' values than previous measurements for most v' levels and lower J' values for v' = 0. We confirm previously observed perturbations of the rotational levels in greater detail and present evidence for new perturbations. The accuracy in the wavelength determination and term values is on average within 0.01 cm(-1), improving upon previous measurements.

Rotationally cold absorption and two-photon ionization spectra of CO in the 90-100 nm region have been recorded at a resolution of 0.3-1.0 cm(-1). The analyses of up to four isotopomers seek to clarify the observations in regions where the Rydberg levels built on the ground state X (2)Sigma(+) of the ion interact with valence states of (1)Sigma(+) and (1)Pi symmetry. Previous observations of the 3ssigma, B (1)Sigma(+) Rydberg state, reviewed by Tchang-Brillet et al. [J. Chem. Phys. 96, 6735 (1992)], have been extended to energies above its avoided crossing with the repulsive part of the D(') (1)Sigma(+) valence state where resonances of varying intensities and widths have been attributed to the fully coupled 3ssigma or 4ssigma and D(') potentials, and where the B state approaches a second avoided crossing with the C(') (1)Sigma(+) valence state [Cooper and Kirby, J. Chem. Phys. 87, 424 (1987); 90, 4895 (1989); Chem. Phys. Lett. 152, 393 (1988)]. Fragments of a progression of weak and mostly diffuse bands, observed for all four isotopomers, have been assigned to the C(')<--X transition. The least-squares modeling of the 4p and 5p complexes reveals the 3ppi, E (1)Pi Rydberg state to be one of the perturbers, violating the Deltav=0 selection rule for Rydberg-Rydberg interactions on account of its rapid transition with increasing v from Rydberg to valence state. A second (1)Pi perturber, very loosely bound and clearly of valence type, contributes to the confusion in the published literature surrounding the 5p, v=0 complex., ((c) 2004 American Institute of Physics.)

The forbidden c(3)Pi-X(1)Sigma(+) (0-0) absorption band of carbon monoxide has been reinvestigated under different pressure conditions using the 10.7-m VUV spectrograph at Meudon. Overlap with the allowed C(1)Pi-X(1)Sigma(+) (0-0) band at lower transition energy has been taken into account. We have identified a new rotational branch corresponding to an S-type branch and extended the analysis to both higher and lower J. An analysis of the band structure and the low J transition lines suggests that the band gains its intensity predominantly as a result of an interaction of the c(3)Pi state with a (1)Sigma(+) state, most likely the C(1)Sigma(+) (v = 0) state. Molecular constants have been obtained for the c(3)Pi state that are in reasonable agreement with those previously published. The apparently anomalous small value for the centrifugal distortion constant is explained by a homogeneous perturbation with the k(3)Pi valence state. Copyright 2000 Academic Press.