Research Article

Ultrafast Dynamics of Solute-Solvent Complexation Observed at Thermal Equilibrium in Real Time

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Science  26 Aug 2005:
Vol. 309, Issue 5739, pp. 1338-1343
DOI: 10.1126/science.1116213

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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.

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