Interaction of TiO+ with water: infrared photodissociation spectroscopy and density functional calculations

Abstract

We investigated the interaction of TiO(+) with water by conducting infrared photodissociation spectroscopy and density functional theory calculations on TiO(H2O)Ar(+) and TiO(H2O)5-7(+) clusters. The studies show that TiO(H2O)Ar(+) has two isomers, Ti(OH)2Ar(+) and (H2O)-TiOAr(+), coexisting in our experiments. The structure of TiO(H2O)5(+) is characterized by attaching four water molecules to a Ti(OH)2(+) core with their O atoms interacting with the Ti atom directly. With the increasing number of water molecules, the additional water molecules start to form hydrogen bonds with the inner shell water molecules and the OH groups of Ti(OH)2(+) instead of coordinating directly with the Ti atom. Therefore, the structures of TiO(H2O)6(+) and TiO(H2O)7(+) clusters are evolved from that of TiO(H2O)5(+) by adding the sixth and seventh water molecules to the second solvent-shell. Our results demonstrate that a Ti(OH)2(+) type of product is dominant when TiO(+) interacts with water, especially when more water molecules are involved.

Experimental and theoretical studies of H2O oxidation by neutral Ti2O4,5 clusters under visible light irradiation

“…Infrared photodissociation spectroscopy and density functional theory (DFT) calculations of the interaction of TiO + with water, demonstrate that a Ti(OH) 2 + type product is dominant for this process. 42 The structure of neutral (TiO 2 ) n (n = 2-13) clusters 43 and reliable values for the heats of formation of small (TiO 2 ) n (n = 1-3) clusters 44 have been reported. These structures and energies can be useful for understanding the general chemistry of (TiO 2 ) n species.…”

“…Numerous experimental [25][26][27][28][29][30][31][32] and theoretical [33][34][35][36][37][38][39][40][41][42] studies have been reported for isolated, neutral and charged titanium oxide clusters with the intent of correlating their structures and properties with those of the bulk. For example, Zhai et al 25 have studied the electronic structure and band gap evolution of (TiO 2 ) n À (n = 1-10) clusters, employing photoelectron spectroscopy, to gain mechanistic understanding of TiO 2 surface defects and photo-catalytic properties.…”

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

“…[49][50][51][52][53] There has been substantial progress made in understanding the structure and reactivity of small metal oxide clusters, [54][55][56][57][58][59] including several studies on the interaction between titanium dioxide clusters and water molecules. [60][61][62][63] Of particular relevance is the work of Zheng and co-workers, who performed anion photoelectron spectroscopy (PES) on the anionic (TiO 2 )(H 2 O) 0-7 clusters and inferred that dissociative adsorption of water occurs to form a hydroxide species. 61 We recently reinvestigated the (TiO -2 )(H 2 O) system using slow electron velocity-map imaging of cryogenically cooled anions (cryo-SEVI), a high-resolution form of anion PES, coupled with detailed computational simulations.…”

Interaction of TiO2− with water: Photoelectron spectroscopy and density functional calculations

“…33,34 Since atomic and molecular clusters can be regarded as models for understanding the fundamental mechanisms in condensed phases and on complex surfaces, numerous studies have been carried out to investigate the hydrated metal-oxide clusters and their corresponding isomers. [35][36][37][38][39] These studies suggested that metal oxides interacting with water can form hydrated metal-oxides or under water dissociation to produce the corresponding hydroxyl species. Recently, we have investigated the interaction of Co n O − with water and found that they prefer to exist in the form of Co n (OH) 2 (H 2 O) n − .…”