Energy Insights on Dissociative Chemisorption of (H 2O) n=1,2,3 on Rutile‐TiO 2(110)

ABSTRACT In this work, dissociative chemisorption of (HO), , on Rutile(R)‐TiO(110) was systematically studied by computing initial‐geometry‐specific potential energy curves (PECs) through the Perdew‐Burke‐Ernzerhof (PBE) exchange‐correlation functional. Due to orientational hydrogen‐bonding interactions, (HO) adsorbs on oxygen sites if it approaches to surface with the appropriate conformation. In general, the water molecule preferentially chemisorbs on the five‐fold titanium atom (Ti) but never adsorbs on the six‐fold one (Ti), while the second water molecule again preferentially chemisorbs on the nearest Ti atom. This is consistent with experimental measurements ( Chem. Soc. Rev. 45 (2016), 3701 and Chem. Rev. 119 (2019), 11020). Moreover, PECs for the dissociations of various O‐H bonds are computed. The dissociation barriers with imply that dissociation ability increases with the increase of . This is different from experiments on photon‐dissociation ( Chem. Rev. 119 (2019), 11020) which experimentally indicated that water dimer (i.e., ) has the largest photon‐dissociation probability. This discrepancy between calculation and experiment implies the necessity of non‐adiabatic quantum dynamics based on new potential energy surfaces, because the previous experiments focused on the photon‐dissociation of (HO) on R‐TiO(110) with . Based on the present PBE calculations, discussions on previous experiments and calculations are also given.