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Journal of Physical Chemistry A, Vol.108, No.13, 2559-2566, 2004
Effect of pressure on the proton-transfer rate from a photoacid to a solvent. 2. 2-Naphthol-6-sulfonate in water
The reversible proton dissociation and geminate recombination of the photoacid 2-naphthol-6-sulfonate is studied as a function of pressure in liquid water. Our time-resolved experimental data are analyzed by the reversible diffusion-influenced chemical reaction model. The proton-transfer rate increases significantly with pressure. At 10 kbar the rate increases by about a factor of 8. The main pressure effect is the decrease of the distance between the proton donor and acceptor. The pressure dependence is explained using an approximate stepwise two-coordinate proton-transfer model. The increase in rate as a function of pressure manifests the strong dependence of proton tunneling on the distance between the two heavy atoms which decreases with an increase of pressure.