Journal of Chemical Physics, Vol.119, No.7, 3737-3744, 2003
One- and two-color photoelectron imaging of the CO molecule via the B-1 Sigma(+) state
This paper is concerned with photoelectron imaging following one-color (2+1) and two-color (2+1') resonance enhanced multiphoton ionization in the CO molecule. After the two-photon absorption step B (1)Sigma(+) (v(')=0)<--<--X (1)Sigma(+) (v(')=0) or B (1)Sigma(+) (v(')=1)<--<--X (1)Sigma(+) (v(')=0), the subsequent one-photon ionization X (2)Sigma(+)(v(+))<--B (1)Sigma(+) (v(')=0,1) shows deviations from the expected Deltav=0 Franck-Condon propensity rule. The results are in good agreement with a previous study using time-of-flight photoelectron spectroscopy [Sha , J. Chem. Phys. 99, 4334 (1993)]. The experimental photoelectron kinetic energy spectra and their angular distributions are analyzed, and the essential role played by "superexcited" Rydberg states with an A (2)Pi ion core in this process is examined. Moreover, photoelectron imaging methods appear to be useful in extracting information about superexcited states. (C) 2003 American Institute of Physics.