Dissociation Energies of Sulfur-Centered Hydrogen-Bonded Complexes

J Phys Chem A. 2015 Nov 5;119(44):10863-70. doi: 10.1021/acs.jpca.5b08185. Epub 2015 Oct 23.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Computer Simulation*
  • Coordination Complexes / chemistry*
  • Hydrogen / chemistry*
  • Hydrogen Bonding
  • Hydrogen Sulfide / chemistry*
  • Mass Spectrometry
  • Phenol / chemistry
  • Sulfur / chemistry*
  • Thermodynamics*

Substances

  • Coordination Complexes
  • Phenol
  • Sulfur
  • Hydrogen
  • Hydrogen Sulfide