화학공학소재연구정보센터
Journal of Chemical Physics, Vol.116, No.19, 8384-8395, 2002
Laser-assisted (1+1')-photon ionization-detected absorption spectrum of the 3p pi (2)Pi state of HCO and DCO
We re-examine the ionization-detected ultraviolet absorption spectrum of the 3ppi (2)Pi<--X (2)A' transition in HCO and DCO using a high-power visible laser to enhance the observation of first-photon resonant features. This technique, which we term here, assisted REMPI, significantly improves the signal-to-noise ratio of the spectrum, making many weak vibronic sub-bands visible for the first time. A comprehensive fit to the structure evident in a progression of bending levels from (000) to (040) refines the assignment of Song and Cool [X. M. Song and T. A. Cool, J. Chem. Phys. 96, 8664 (1992)] to yield a set of rotational constants that vary with K in relation to v(2), together with a higher-order contribution to the Renner-Teller splitting in HCO, which is mirrored in DCO for all levels but (040). The (040) band falls at a frequency that is commensurate with that of CD stretch, and Fermi resonance between 3ppi (2)Pi(10(0)0)Pi and the higher-energy (040) K=1(Pi) component gives rise to an added splitting that increases the energy of this (040) component and causes an apparent increase in the Renner parameter.