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Abstract
The lowest few gerade Rydberg states of C2H2, C2HD, and C2D2 have been observed as two‐photon resonances in the multiphoton ionization (MPI) spectra of these isotopic species. Analysis of the two‐photon excitation spectra of these molecules, and of the accompanying MPI‐photoelectron spectra for C2H2, enable characterization of the 1Σ+g and 1Δg Rydberg states arising from the electronic promotion π3u3pπ1u←π4u and reveal extensive vibronic interaction in this energy region. A search was made for higher gerade Rydberg states at energies up to 90 000 cm−1. Weak, diffuse signal is observed for the 4p complex. No ionization signal was observed in the energy range where the np (n=5–7) Rydberg states are expected to appear. This is taken as evidence for opening of a facile nonradiative decay channel at high excitation energies.
Published Version
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