Photoelectron imaging of propanal by resonant multiphoton ionization via the 3s Rydberg state.

We report the conformationally- and vibrationally-selected photoelectron spectroscopy of propanal obtained by resonance-enhanced multiphoton ionization (REMPI) using photoelectron imaging. These photoelectron spectra, employing (2 + 1) ionization via the (n, 3s) Rydberg transitions in the range from 365 to 371 nm, confirm that there are two stable conformer origins in the lowest ionic state, the cis conformer with a co-planar CCCO geometry and a gauche conformer with a approximately 119 degrees CCCO dihedral angle. From ab initio calculations at the B3LYP/6-311++G** level, we find the gauche conformer is slightly more stable, with the energy difference between two conformers determined to be only 65 cm(-1). In our photoelectron spectra, the vertical ionization potential (IP) for the cis conformer of propanal was then determined to be 9.999 (+/-0.003) eV, while that of the gauche conformer of propanal was estimated to be 9.944 eV. A long vibrational progression in the in-plane CCCO deformation vibrational mode, v, for the cis conformer is systematically observed in all photoelectron spectra in which this mode is excited, suggesting that the geometry of the ground ionic state is significantly different from that of the 3s Rydberg state, particularly along the v(15) coordinates.