Zero kinetic energy spectroscopy of hydroquinone-water (1:1) complex: A probe for conformer assignment

Abstract

Zero kinetic energy (ZEKE) photoelectron spectroscopy of the hydroquinone-water (HQW) complex was carried out to characterize its 𝑆1-𝑆0 resonantly enhanced multiphoton ionization (REMPI) spectrum in terms of the cis and trans conformers. The ZEKE spectra of the hydroquinone isomers show differences in the Franck-Condon (FC) activity of a few ring modes, viz., modes 15, 9𝑏, and 6𝑏, due to the different symmetries of the two isomers. These modes were used as a “diagnostic tool” to carry out the categorical assignment of the REMPI spectrum of the HQW complex. It was found that the FC activity of these diagnostic modes in the cationic ground state (𝐷0) of the water complex is similar as that of the monomer. The two lowest energy transitions in the REMPI spectrum of the water complex, 33 175 and 33209cm−1, were reassigned as the band origins of the cis and trans hydroquinone-water complexes, which is opposite of the previous assignment. The intermolecular stretching mode (𝜎) of the complex shows a long progression, up to 𝑣′=4, in the cationic ground state and is strongly coupled to other observed ring modes. The Franck-Condon factors for different members in the progression were calculated using the potential energy surfaces computed ab initio. These agree well with the observed intensity patterns in the progression. The ionization potential of the trans and cis complexes was determined to be 60071±4 and 60024±4cm−1, respectively