Rovibrational-state-selected photoionization of acetylene by the two-color IR+VUV scheme: observation of rotationally resolved Rydberg transitions.

We have demonstrated a rovibrational-state-selected photoionization experiment using an IR laser and high-resolution VUV-synchrotron radiation. The VUV photoionization of acetylene [C2H2(Xtilde; (1)Sigma(+)(g);nu(3)=1,J(')=8 or 10)] prepared by IR excitation reveals three strong autoionizing Rydberg series converging to C2H+2(Xtilde; (2)Pi(u);nu(+)(3)=1) with little ion background interference. Rotational transitions resolved for the Rydberg states provide an estimate of approximately 1.8 ps for their lifetimes. This experiment opens the way for state-selective photoionization studies of polyatomic molecules using VUV-synchrotron radiation.