Rotational analysis for the Doppler-free photoelectron spectrum of water using the spectator model.

A photoelectron spectrum of H(2)O has been recorded at a resolution of 2 meV under Doppler-free conditions. Complex rotational structures appear in the individual vibrational states of the electronic X̃(+ 2)B(1) and Ã(+ 2)A(2) states in H(2)O(+). The rotational structures are analyzed and well reproduced using a spectator orbital model developed for rotationally resolved photoelectron spectroscopy.