Zero-kinetic-energy photoelectron spectroscopy of the hydrogen-bonded phenol-water complex

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Abstract
Two‐photon, two‐color (1+1’) zero‐kinetic‐energy (ZEKE) photoelectron spectra are presented for the 1:1 phenol‐water complex, a prototype system for hydrogen bonding between an aromatic molecule and a simple solvent. ZEKE spectra via different (intermolecular) vibrational intermediate S 1 levels of the fully protonated complex (C6H5OH–H2O, h 3) as well as the ZEKE spectrum via the vibrationless S 1 state of the threefold deuterated complex (C6H5OD–D2O, d 3) have been recorded. The spectra are rich in structure, which is mainly attributable to intermolecular vibrations of the ionic complex. Progressions of the intermolecular stretch vibration (240 cm−1) in combination with different intermolecular and intramolecular vibrational levels are the dominant feature of all ZEKE spectra obtained and indicate a large change in the complex geometry along the hydrogen‐bond coordinate on ionization. Comparison between the spectrum of the d 3 complex and the spectra via different intermediate intermolecular levels of the h 3 complex has allowed a more detailed analysis of the intermolecular features compared to previously reported results. Finally, the vibrational assignments obtained are compared with ab initio results for the phenol‐water cation reported in the following paper in this issue.

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