The mechanisms and energetics of the formation of various defects upon dehydration of the surface of pure-siliceous and Al-monosubstituted mordenite are investigated using a periodic ab initio density functional theory technique. An energetically favorable defect at the pure-siliceous surface is a strained two-membered Si-O ring (2MR) formed via elimination of a water molecule from a pair of neighboring terminal silanol groups. Assuming the formation of two-membered rings, the dehydration-energy of the (001) surface of pure-silica mordenite is 133 kJ/mol. A relatively high reaction barrier of 179 kJ/mol coincides with the experimental observation that these defects are formed at high temperatures >700 K. Despite a short Si-Si distance of 2.35 A across the 2MR which is comparable to the bond length between Si atoms in silicon in diamond structure, the electron-localization function reveals no bonding interaction between Si atoms on the 2MR. In the Al-substituted surfaces, the dehydration proceeds via proton transfer from the Bronsted-acid site (BA) to a neighboring terminal hydroxyl group. The low values of two subsequent energetic barriers of dehydration of 13 and 10 kJ/mol suggest that the surface BA sites are likely to be destroyed at even modest temperatures. The most stable defects formed in this mechanism are ones containing a threefold-coordinated Al atom and a defect with both an Al atom and a bridging OH group located on a two-membered ring. The heat of reaction of only 9 kJ/mol and the activation energy of the transformation between these two configurations of 26 kJ/mol suggest that both defects occur with similar probability. (C) 2003 American Institute of Physics.