S 1 excitation and zero kinetic energy spectra of partly deuterated 1:1 phenol–water complexes

Abstract

Two-photon, two-color resonant-enhanced multiphoton ionization (REMPI) spectra of the S1 state of isotopic 1:1 hydrogen-bonded phenol–water clusters have been recorded. Up to three deuterium atoms are introduced in the phenolic OH group and/or the water molecule. The intermolecular vibrational structure found is in reasonable agreement with previously reported one-color REMPI spectra, however, a partly different interpretation of the spectra is presented here. Zero kinetic energy photoelectron (ZEKE) spectra have been obtained via different intermediate S1 levels of the various isotopic complexes. The analysis of both the REMPI and the ZEKE spectra supports the new assignment of several vibrational bands observed in the REMPI spectra of the deuterated complexes where one or two hydrogen atoms are substituted by deuterium. For these deuterated complexes, the reassignment given here is based on the assumption that two different nonequivalent isomeric configurations are responsible for the structure observed in the REMPI spectra. This result is in clear contrast to the previously given interpretation where the spectra were analyzed in terms of only one isomer and the occurrence of Fermi resonances. Furthermore, accurate ionization energies are determined for all possible isomers of the various isotopic complexes and propensity rules for these values as a function of site-specific deuteration have been found. In addition, the analysis of the intermolecular vibrational structure of the complex cations confirmed the assignment of the intermolecular stretch vibration.