Physics: Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time

Junrong Zheng, Kyungwon Kwak, John Asbury, Xin Chen, Ivan R. Piletic, M. D. Fayer

Research output: Contribution to journalArticle

362 Scopus citations

Abstract

In general, the formation and dissociation of solute-solvent complexes have been too rapid to measure without disturbing the thermal equilibrium. We were able to do so with the use of two-dimensional infrared vibrational echo spectroscopy, an ultrafast vibrational analog of two-dimensional nuclear magnetic resonance spectroscopy. The equilibrium dynamics of phenol complexation to benzene in a benzene-carbon tetrachloride solvent mixture were measured in real time by the appearance of off-diagonal peaks in the two-dimensional vibrational echo spectrum of the phenol hydroxyl stretch. The dissociation time constant τd for the phenol-benzene complex was 8 picoseconds. Adding two electron-donating methyl groups to the benzene nearly tripled the value of τd and stabilized the complex, whereas bromobenzene, with an electron-withdrawing bromo group, formed a slightly weaker complex with a slightly lower τd. The spectroscopic method holds promise for studying a wide variety of other fast chemical exchange processes.

Original languageEnglish (US)
Pages (from-to)1338-1343
Number of pages6
JournalScience
Volume309
Issue number5739
DOIs
StatePublished - Aug 26 2005

All Science Journal Classification (ASJC) codes

  • General

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