Synchrotron-based photoemission spectroscopy and low-energy electron diffraction were used to study the reaction of water vapor at 300 K and different water vapor pressures, p(H2O), ranging from 5 x 10(-9) Torr to 10(-3) Torr (3 min exposure at each pressure), with vacuum-cleaved MgO(100) surfaces that had low (5-10%) defect densities. The O 1s, Mg 2p, and O 2s/VB spectra were acquired at photon energies chosen to optimize surface sensitivity. O 1s and O 2s/VB spectra are sensitive to water adsorption onto MgO(100) even at very low water vapor exposures [<10(-8) Torr for 3 min (<1.8 L)], whereas Mg 2p spectra show significant changes only for high exposures [greater than or equal to 10(-4) Torr for 3 min (greater than or equal to 1.8 x 10(4) L)]. Comparison of these spectra with similar spectra of MgO(100) surfaces immersed in bulk water and of polycrystalline Mg(OH)(2) indicates that water chemisorbs dissociatively in two distinct stages on "low defect" MgO(100) surfaces, forming surface hydroxyl groups. The first stage occurs at water vapor exposures less than or equal to 3 x 10(-5) Torr for 3 min (less than or equal to 5.4 x 10(3) L) or for 30 min (less than or equal to 5.4 x 10(4) L) and involves a relatively fast reaction with surface defects (corner and edge-step sites and point defects) comprising 5-10% of the surface sites, in agreement with recent first-principles electronic structure calculations. The second stage occurs at higher water vapor pressures (>10(-4) Torr for 3 min) and involves dissociative chemisorption of water on terrace sites, which is not predicted by recent first-principles calculations. The apparent sticking coefficient for the first reaction stage (greater than or equal to 0.16) is about four orders of magnitude larger than that for the second reaction stage (greater than or equal to 3 x 10(-5)), suggesting that the second reaction stage requires significantly more activation energy than the first stage. Our results also suggest that the hydroxylation reaction is not sensitive to exposure time below a threshold pressure of approximate to 10(-4) Torr. Although both kinetic and thermodynamic interpretations are possible, a thermodynamic analysis of the hydroxylation reaction (using bulk solid free energies) predicts approximately the same threshold pressure as observed. After the surface is fully hydroxylated, additional water can be physisorbed on the hydroxyl layer. Analysis of O 1s spectra taken from the same surface but at different photon energies indicates that hydroxyls are formed predominantly on the surface and not in the bulk under these exposure conditions. Our experimental data also show that the 4-6 eV electrons used to mitigate surface change during the photoemission experiments have no effect on the dissociation of water on the MgO(100) surface. (C) 1998 Elsevier Science B.V. All rights reserved.