Vibrational deactivation of surface OH chemisorbed on SiO2: Solvent effects

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Abstract
Picosecond infrared transmission spectroscopy was used to directly measure the vibrational energy relaxation time T1 of hydroxyl groups chemisorbed on the surface of colloidal silica (SiO2). T1 was obtained for OH(νstretch=1) in the strongly bound ‘‘isolated sites’’ of fumed silica particles in vacuum and dispersed in several liquids at T=293 K. At the SiO2/vacuum interface, T1=204±20 ps. When the SiO2 particles are surrounded by solvents, the relaxation time of the surface OH(v=1) groups decreases: for the liquids CCl4, CF2Br2, CH2Cl2, and C6H6, T1(ps)=159±16, 140±30, 102±20, and 87±30, respectively. T1 does not depend on the size of the SiO2 particles for the range 70 Å≤ diameter ≤150 Å, or on the surface OH coverage up to an average density of 4 OH/100 Å2. Significant amounts of physisorbed water (5 H2O/100 Å2) decreased T1 for the isolated OH(v=1) to T1=56±10 ps. For comparison to the surface hydroxyls, the vibrational deactivation time for OH(v=1) groups in the bulk of fused silica (OH/SiO2≊130 ppm by weight) was determined to be T1=109±11 ps. These observations are discussed in terms of the possible mechanisms of vibrational energy flow in these systems. The observed T1 values demonstrate that the spectral linewidths (e.g., IR and Raman) observed for these surface vibrations are too large (by factors of 200–2000) to be caused solely by T1 uncertainty broadening. The slow transfer of vibrational energy between surface and lattice vibrations may have important implications for surface chemistry.