caa a22 4500 605512647 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2633-1 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2633-1 The N2O activation by Rh5 clusters. A quantum chemistry study [Elektronische Daten] [Oscar Olvera-Neria, Roberto Avilés, Héctor Francisco-Rodríguez, Virineya Bertin, Raúl García-Cruz, Julio González-Torres, Enrique Poulain] Nitrous oxide (N2O) is a by-product of exhaust pipe gases treatment produced by motor vehicles. Therefore, the N2O reduction to N2 is necessary to meet the actual environmental legislation. The N2O adsorption and dissociation assisted by the square-based pyramidal Rh5 cluster was investigated using the density functional theory and the zero-order regular approximation (ZORA). The Rh5 sextet ground state is the most active in N2O dissociation, though the quartet and octet states are also active because they are degenerate. The Rh5 cluster spontaneously activates the N2─O cleavage, and the reaction is highly exothermic ca. -75kcal mol-1. The N2─O breaking is obtained for the geometrical arrangement that maximizes the overlap and electron transfers between the N2O and Rh5 frontier orbitals. The Rh5 high activity is due to the Rh 3d orbitals are located between the N2O HOMO and LUMO orbitals, which makes possible the interactions between them. In particular, the O 2p states strongly interact with Rh 3d orbitals, which finally weaken the N2─O bond. The electron transfer is from the Rh5 HOMO orbital to the N2O antibonding orbital. Graphical Abstract N2O activation by Rh5 clustersᅟ Springer-Verlag Berlin Heidelberg, 2015 Density functional theory nationallicence Excited states nationallicence N2O activation nationallicence Spin states nationallicence Transition metal clusters nationallicence Olvera-Neria Oscar Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut Avilés Roberto Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut Francisco-Rodríguez Héctor Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, 09340, Mexico, D. F., Mexico aut Bertin Virineya Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, 09340, Mexico, D. F., Mexico aut García-Cruz Raúl Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut González-Torres Julio Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut Poulain Enrique Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2633-1 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2633-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Olvera-Neria Oscar Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut NATIONALLICENCE 700 1- Avilés Roberto Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut NATIONALLICENCE 700 1- Francisco-Rodríguez Héctor Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, 09340, Mexico, D. F., Mexico aut NATIONALLICENCE 700 1- Bertin Virineya Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina, 09340, Mexico, D. F., Mexico aut NATIONALLICENCE 700 1- García-Cruz Raúl Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut NATIONALLICENCE 700 1- González-Torres Julio Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut NATIONALLICENCE 700 1- Poulain Enrique Área de Física Atómica Molecular Aplicada (FAMA), CBI, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, 02200, Mexico, D. F., Mexico aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894