title: Dissociation Energies of Sulfur-Centered Hydrogen-Bonded Complexes.
abstract: In this work we have determined dissociation energies of O-H···S hydrogen bond in the H2S complexes of various phenol derivatives using 2-color-2-photon photofragmentation spectroscopy in combination with zero kinetic energy photoelectron (ZEKE-PE) spectroscopy. This is the first report of direct determination of dissociation energy of O-H···S hydrogen bond. The ZEKE-PE spectra of the complexes revealed a long progression in the intermolecular stretching mode with significant anharmonicity. Using the anharmonicity information and experimentally determined dissociation energy, we also validated Birge-Sponer (B-S) extrapolation method, which is an approximate method to estimate dissociation energy. Experimentally determined dissociation energies were compared with a variety of ab initio calculations. One of the important findings is that ωB97X-D functional, which is a dispersion corrected DFT functional, was able to predict the dissociation energies in both the cationic as well as the ground electronic state very well for almost every case.
authors.affiliation: Department of Chemical Sciences, Tata Institute of Fundamental Research , Homi Bhabha Road, Colaba, Mumbai 400 005, India.
authors.forename: Sanat
authors.initials: S
authors.lastname: Ghosh
authors.affiliation: Department of Chemical Sciences, Tata Institute of Fundamental Research , Homi Bhabha Road, Colaba, Mumbai 400 005, India.
authors.forename: Surjendu
authors.initials: S
authors.lastname: Bhattacharyya
authors.affiliation: Department of Chemical Sciences, Tata Institute of Fundamental Research , Homi Bhabha Road, Colaba, Mumbai 400 005, India.
authors.forename: Sanjay
authors.initials: S
authors.lastname: Wategaonkar
mesh_terms: D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D006862:Hydrogen Sulfide / Q000737:chemistry*; D013058:Mass Spectrometry; D019800:Phenol / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D019800:Phenol; D013455:Sulfur; D006859:Hydrogen; D006862:Hydrogen Sulfide