Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions

Ehud Pines, Dina Pines, Ying Zhong Ma, Graham R. Fleming

Research output: Contribution to journalArticlepeer-review

80 Scopus citations


An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the salvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 ± 10 fs solvation response was found to be about 35% and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H⋯O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.

Original languageEnglish
Pages (from-to)1315-1327
Number of pages13
Issue number9
StatePublished - 20 Sep 2004


  • Femtochemistry
  • Hydrogen-bonding interactions
  • Photoacids
  • Pump-probe spectroscopy
  • Solvation dynamics

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry


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