Document Type

Article

Original Publication Date

2008

Journal/Book/Conference Title

The Journal of Chemical Physics

Volume

129

Issue

7

DOI of Original Publication

10.1063/1.2969108

Comments

Originally published at http://dx.doi.org/10.1063/1.2969108

Date of Submission

October 2015

Abstract

Using first-principles calculations based on gradient corrected density functional theory, we have studied the interaction of NH3, H2, and O2 with Ti-benzene complexes [Ti(Bz)2 and Ti2(Bz)2]. The energy barriers as the gas molecules approach the Ti-benzene complexes as well as the geometries of the ground state of these interacting complexes were obtained by starting with several initial configurations. While NH3 and H2 were found to physisorb on the Ti(Bz)2 complex, the O2 reacts with it strongly leading to dissociative chemisorption of the oxygen molecule. In contrast all the gas molecules react with the Ti2(Bz)2 complex. These studies indicate that the reaction of certain, but not all, gas molecules can be used to probe the equilibrium geometries of organometallic complexes. Under special conditions, such as high pressure, the Ti atom intercalated between benzene molecules in Ti(Bz)2 and the Ti2(Bz)2 complexes could store hydrogen in chemisorbed states. The results are compared to available experimental data.

Rights

Chen, G., Jena, P., Kawazoe, Y. Interaction of gas molecules with Ti-benzene complexes. The Journal of Chemical Physics 129, 074305 (2008). Copyright © 2008 AIP Publishing LLC.

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