The Cl(2p) photoelectron spectra of the HCl and DCl molecules:: the effects of the molecular field

The Cl(2p) photoelectron spectra of HCl and DCl have been measured with high resolution. Careful data analysis with a least-squares fitting method enabled us to determine the spectroscopic parameters for the three spin-orbit and molecular field split components of the Cl(2p)(-1) states. The experimental results were compared with ab initio calculations. The values of 84 +/- 9 meV, 71 +/- 13 meV, and 103 +/- 10 meV for the lifetime line widths of (2)Pi(1/2), (2)Sigma(1/2)(+), and (2)Pi(3/2) states were extracted from the experiment. An anomalous photoionization cross section ratio (60%) between the (2)Sigma(1/2)(+) and (2)Pi(3/2) states was observed.