Journal article
O―H···S Hydrogen Bonds Conform to the Acid―Base Formalism
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.117(34), pp.8238-8250
2013
DOI: 10.1021/jp405414h
PMID: 23947570
Abstract
Hydrogen bonding interaction between the ROH hydrogen bond donor and sulfur atom as an acceptor has not been as well characterized as the O-H⋯O interaction. The strength of O-H⋯O interactions for a given donor has been well documented to scale linearly with the proton affinity (PA) of the H-bond acceptor. In this regard, O-H⋯O interactions conform to the acid-base formalism. The importance of such correlation is to be able to estimate molecular property of the complex from the known thermodynamic data of its constituents. In this work, we investigate the properties of O-H⋯S interaction in the complexes of the H-bond donor and sulfur containing acceptors of varying proton affinity. The hydrogen bonded complexes of p-Fluorophenol (FP) with four different sulfur containing acceptors and their oxygen analogues, namely H2O/H2S, MeOH/MeSH, Me2O/Me 2S and tetrahydrofuran (THF)/tetrahydrothiophene (THT) were characterized in regard to its S1-S0 excitation spectra and the IR spectra. Two-color resonantly enhanced multiphoton ionization (2c-R2PI), resonant ion-dip infrared (RIDIR) spectroscopy, and IR-UV hole burning spectroscopic techniques were used to probe the hydrogen bonds in the aforementioned complexes. The spectroscopic data along with the ab initio calculations were used to deduce the strength of the O-H⋯S hydrogen bonding interactions in these system relative to that in the O-H⋯O interactions. It was found that, despite being dominated by the dispersion interaction, the O-H⋯S interactions conform to the acid-base formalism as in the case of more conventional O-H⋯O interactions. The dissociation energies and the red shifts in the O-H stretching frequencies correlated very well with the proton affinity of the acceptors. However, the O-H⋯S interaction did not follow the same correlation as that in the O-H⋯O H-bond. The energy decomposition analysis showed that the dissociation energies and the red shifts in the O-H stretching frequencies follow a unified correlation if these two parameters were correlated with the sum of the charge transfer and the exchange component of the total binding energy. © 2013 American Chemical Society.
Details
- Title: Subtitle
- O―H···S Hydrogen Bonds Conform to the Acid―Base Formalism
- Creators
- Surjendu Bhattacharyya - Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400 005, Mumbai, IndiaAditi Bhattacherjee - Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400 005, Mumbai, IndiaPranav R Shirhatti - Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400 005, Mumbai, IndiaSanjay Wategaonkar - Department of Chemical Sciences, Tata Institute of Fundamental Research, Homi Bhabha Road, Colaba, Mumbai 400 005, Mumbai, India
- Resource Type
- Journal article
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.117(34), pp.8238-8250
- Publisher
- American Chemical Society
- DOI
- 10.1021/jp405414h
- PMID
- 23947570
- ISSN
- 1089-5639
- eISSN
- 1520-5215
- Language
- English
- Date published
- 2013
- Academic Unit
- Chemistry
- Record Identifier
- 9984216708902771
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