The speciation of water and hydroxyl groups bound to the surface of a nanoc
rystalline titania film has been investigated by in-situ infrared spectrosc
opy as a function of temperature. Calibration of the absorbance of the delt
a (H2O) mode at 1625 cm(-1) by thermogravimetry has enabled an estimation o
f the concentration of surface H2O present during thermal dehydration of th
e films, which varied from 5 to 0.65 molecules per nm(2) over the temperatu
re range 27-150 degreesC. Two types of coordinated H2O and both terminally
bound and nm bridging hydroxyls have been identified by the temperature-dep
endent behavior of their corresponding O-H stretching modes. Hydrogen bondi
ng was observed between coordinated H2O and terminally bound hydroxyls (v(O
H) = 3730 cm(-1)), whereas bridging hydroxyls (v(OH) = 3670 cm(-)1) do not
appear to be affected by similar H-bonding.