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Novel theoretical studies of the dehydrogenation of LiBH 2 NH 3
Author(s) -
Wang Kun,
Zhang JianGuo,
Man TianTian,
Wu Man,
Zhang ShaoWen,
Zhang TongLai,
Yang Li
Publication year - 2012
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24304
Subject(s) - dehydrogenation , chemistry , alkali metal , quantum tunnelling , perturbation theory (quantum mechanics) , transition state theory , basis set , computational chemistry , transition state , thermodynamics , reaction rate constant , density functional theory , physics , quantum mechanics , kinetics , organic chemistry , catalysis
It is believed that the dehydrogenation of LiNH 2 BH 3 (LAB) proceeds through a combination of the decomposition of the LiBH 2 NH 3 (LBA) and LAB isomers. The dehydrogenation of LBA, an isomer of LAB, is discussed in this article. It is demonstrated that the loss of H 2 from LBA takes place in a two‐step reaction. Studies of the dehydrogenation process were performed using Møller–Plesset second‐order perturbation theory with a 6‐311++G(3df,2pd) basis set. The intrinsic reaction coordinate was calculated to determine the minimum energy paths. Finally, the rate constants were obtained using the transition‐state theory (TST), TST/Eckart, canonical variational transition‐state theory (CVT), CVT/small‐curvature tunneling correction, and CVT/zero‐curvature tunneling correction methods from 200 to 2500 K. This is the first report on a different dehydrogenation mechanism for an alkali‐metal amidoborane, and the energy barrier of LBA is much lower than that of the traditionally studied LAB. © 2012 Wiley Periodicals, Inc.