Toward an Understanding of the Hydrogenation Reaction of MO2 Gas-Phase Clusters (M = Ti, Zr, and Hf)
View/ Open
Impact
Scholar |
Other documents of the author: González Navarrete, Patricio; Calatayud Antonino, Mónica; Andres, Juan; Ruipérez, F.; Roca Sanjuan, Daniel
Metadata
Show full item recordcomunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONMetadata
Title
Toward an Understanding of the Hydrogenation Reaction of MO2 Gas-Phase Clusters (M = Ti, Zr, and Hf)Author (s)
Date
2013Publisher
American Chemical SocietyISSN
1089-5639; 1520-5215Bibliographic citation
GONZALEZ-NAVARRETE, Patricio, et al. Toward an Understanding of the Hydrogenation Reaction of MO2 Gas-Phase Clusters (M= Ti, Zr, and Hf). The Journal of Physical Chemistry A, 2013, vol. 117, no 25, p. 5354-5364.Type
info:eu-repo/semantics/articlePublisher version
http://pubs.acs.org/doi/ipdf/10.1021/jp4033589Version
info:eu-repo/semantics/acceptedVersionSubject
Abstract
A theoretical investigation using density functional theory (DFT) has been carried out in order to understand the molecular mechanism of dihydrogen activation by means of transition metal dioxides MO2 (M = Ti, Zr, and ... [+]
A theoretical investigation using density functional theory (DFT) has been carried out in order to understand the molecular mechanism of dihydrogen activation by means of transition metal dioxides MO2 (M = Ti, Zr, and Hf) according to the following reaction: MO2 + H-2 -> MO + H2O. B3LYP/6-311++G(2df,2pd)/SDD methodology was employed considering two possible reaction pathways. As the first step hydrogen activation by M=O bonds yields to metal-oxo hydride intermediates O=MH(OH). This process is spontaneous for all metal dioxides, and the stability of the O=MH(OH) species depends on the transition metal center. Subsequently, the reaction mechanism splits into two paths: the first one takes place passing through the M(OH)(2) intermediates yielding to products, whereas the second one corresponds to direct formation of the product complex OM(H2O). A two-state reactivity mechanism was found for the TiO2 system, whereas for ZrO2 and HfO2 no spin-crossing processes were observed. This is confirmed by CASSCF/CASPT2 calculations for ZrO2 that lead to the correct ordering of electronic states not found by DFT. The results obtained in the present paper for MO2 molecules are consistent with the observed reactivity on surfaces. [-]
Is part of
The Journal of Physical Chemistry A, 2013, vol. 117, no 25Rights
Copyright © 2013 American Chemical Society
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/openAccess
http://rightsstatements.org/vocab/InC/1.0/
info:eu-repo/semantics/openAccess
This item appears in the folowing collection(s)
- QFA_Articles [829]