Two-dimensional photoelectron spectroscopy of acetylene: Rydberg-valence interaction between the (3σg)−1(3pσu)1 and (3σg)−1(3σu)1 states

Abstract

Two-dimensional photoelectron spectroscopy is performed for studying autoionization of acetylene in the Franck–Condon gap between the X 2Πu and A 2Ag states of C2H2+. The photoelectron spectrum in the photon energy range from 12.8 to 13.6 eV shows exclusive vibrational excitation of the symmetric C–H stretching mode ν1 of C2H2+(X 2Πu), which results from autoionization of the valence state (3σg)−1(3σu)1. Vibrational frequencies with anharmonicities of the ν1 and ν2 (the symmetric C–C stretch) modes are determined by a least-squares fit of the ionization energies of the observed peaks to a second order expansion. At the photon energy of 14.120 eV, autoionization of the Rydberg state (3σg)−1(3pπu)1 leads to a complicated photoelectron spectrum where probably the trans-bending mode ν4 of C2H2+(X 2Πu) as well as ν1 is excited, reflecting a substantial geometrical change during autoionization. Furthermore, a similar excitation of the ν4 mode is observed at ∼13.8 eV. An excellent agreement in positions of the vibrational levels between the spectra at 13.821 and 14.120 eV suggests the presence of the Rydberg state (3σg)−1(3pσu)1 at ∼13.8 eV which has not been identified previously in the photoabsorption or photoionization cross section curves. The constant-ionic-state spectra for the ν1=0–4 levels of C2H2+(X 2Πu) show two spectral features: (a) a weak shoulder (v1=0) or a small maximum (ν1=1–4) at 13.8 eV and (b) two groups of peaks in the range of 14.0–14.4 eV. The ratio of the integrated intensity of the 13.8 eV maximum to that of the two groups differs from level to level. This observation is interpreted in terms of a strong interaction between the Rydberg (3σg)−1(3pσu)1 and valence (3σg)−1(3σu)1 states.