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• W2049205832 abstract "The competition between ion-molecule and molecule-molecule interactions was investigated in M+(phenol)2 cluster ions for M=Li, Na, K, and Cs. Infrared predissociation spectroscopy in the O-H stretch region was used to characterize the structure of the cluster ions. By adjusting the experimental conditions, it was possible to generate species where argon was additionally bound in order to investigate cold cluster ions. The spectra showed the presence of hydrogen bonding in the colder M+(phenol)2Ar cluster ions but the absence of hydrogen bonding in the warmer M+(phenol)2 species. For the cold species, the IR spectra were compared with minimum-energy ab initio calculations to elucidate the hydrogen-bonded structures. In the dominant hydrogen-bonded configurations observed experimentally, the phenol molecules form hydrogen-bonded dimers and the alkali-metal ions bind to the phenol via a cation-pi interaction with the aromatic ring. Increasing the strength of the cation-pi interaction by decreasing the ion size forces the distance between the phenol O-H groups to increase, thus weakening the intermolecular hydrogen bond. Free-energy differences of different configurations relative to the ground state demonstrate that hydrogen-bonded structures are enthalpically favored, while non-hydrogen-bonded structures are entropically favored and are thus observed in the warm cluster ions." @default.
• W2049205832 created "2016-06-24" @default.
• W2049205832 creator A5010585224 @default.
• W2049205832 creator A5072496984 @default.
• W2049205832 date "2005-08-15" @default.
• W2049205832 modified "2023-09-26" @default.
• W2049205832 title "Competition between cation-π interactions and intermolecular hydrogen bonds in alkali metal ion-phenol clusters. I. Phenol dimer" @default.
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• W2049205832 doi "https://doi.org/10.1063/1.1995693" @default.
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