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Gas‐phase ammonia activation by Th, Th + , and Th 2+ : Reaction mechanisms, bonding analysis, and rate constant calculations
Author(s) -
Niu Wenxia,
Zhang Hong,
Li Peng,
Gao Tao
Publication year - 2015
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.24753
Subject(s) - chemistry , dehydrogenation , reaction rate constant , exothermic reaction , isomerization , density functional theory , reaction rate , computational chemistry , physics , organic chemistry , catalysis , quantum mechanics , kinetics
The gas‐phase reactions of Th, Th + , and Th 2+ with NH 3 were systematically investigated using different approaches of density functional theory. A detailed description of the reaction mechanisms along with the bonding character analysis offers deep insights into the reaction of Th species. Different possible spin multiplicities were considered as well as the effect of spin‐orbit interactions. The analyses of results indicate that the reactions of Th species with NH 3 have two types of reaction channel: isomerization and dehydrogenation. These dehydrogenation reactions are found to be exothermic, with the best thermochemical conditions observed for Th 2+ +NH 3 . The bonding properties of the species involved in the reaction pathways were investigated by means of diverse analyses including electron localization function, atoms in molecules, and natural bond orbital. Reaction rate constants were computed between 298 and 2000 K at levels of variational transition state theory with the Wigner and Eckart tunneling correction. The computed results are compared with the available experimental values. A comparison with previously studied reactions of Th species with H 2 O and CH 4 as well as U species with NH 3 is performed to obtain similarities and differences of the insertion reactions of actinide atom and cations. © 2014 Wiley Periodicals, Inc.