title: Modeling CO and N2 adsorption at Cr surface species of Phillips catalyst by hybrid density functionals: effect of Hartree-Fock exchange percentage.
abstract: In this article, we present a computational study of the structure and vibrational properties of the species formed by the interaction between Cr sites of Phillips catalyst and probe molecules (CO, N(2)). The vibrational properties of these surface species, intensively investigated in the past, form a very rich and ideal set of experimental data to test computational approaches. By adopting the X(4)Si(2)O(3)Cr (X = H, OH, F) cluster as a simplified model of the ([triple bond]SiO)(2)Cr(II) species present at the surface of the real catalyst, we found that the B3LYP hybrid functional (containing 20% of Hartree-Fock exchange), when applied to this model, is unable to reproduce with reasonable accuracy the currently available experimental data (principally coming from IR spectroscopy). Better agreement is obtained when the percentage of Hartree-Fock exchange is increased (up to 35-40%).
authors.affiliation: Dipartimento di Chimica IFM, and Nanostructured Interfaces and Surfaces Centre of Excellence, University of Torino, Via P.Giuria 7, I-10125 Torino. alessandro.damin@unito.it
authors.forename: Alessandro
authors.initials: A
authors.lastname: Damin
authors.forename: Jenny G
authors.initials: JG
authors.lastname: Vitillo
authors.forename: Gabriele
authors.initials: G
authors.lastname: Ricchiardi
authors.forename: Silvia
authors.initials: S
authors.lastname: Bordiga
authors.forename: Carlo
authors.initials: C
authors.lastname: Lamberti
authors.forename: Elena
authors.initials: E
authors.lastname: Groppo
authors.forename: Adriano
authors.initials: A
authors.lastname: Zecchina