title: L2,3-edges absorption spectra of a 2D complex system: a theoretical modelling.
abstract: L2,3-edges absorption spectra of FePc (I) and FePc(η2-O2) (II) on Ag(110) have been modelled using the DFT/ROCIS method. Despite disregarding the presence of the substrate, the agreement between experiment and theory is remarkable. Moreover, theoretical results confirm the fraction of II (70%) present on the surface, thus allowing a thorough assignment of each experimental spectral feature. Ground state (GS) theoretical outcomes pertaining to I and II provide an intimate understanding of the electron transfer pathway ruling the I-based catalytic oxygen reduction reaction. DFT/ROCIS outcomes indicate that the lower excitation energy (EE) side of the I/IIL3intensity distributions mainly includes states having the GS number of unpaired electrons (two in I and six in II), whereas states with higher/lower spin multiplicity contribute to the I/IIL3higher EE side. The occurrence of states involving metal to ligand charge transfer transitions implying low lying empty π* ligand-based orbitals on the I/IIL3higher EE sides have been confirmed.
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy. maurizio.casarin@unipd.it silvia.carlotto@unipd.it.
authors.forename: S
authors.initials: S
authors.lastname: Carlotto
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy. maurizio.casarin@unipd.it silvia.carlotto@unipd.it.
authors.forename: M
authors.initials: M
authors.lastname: Sambi
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy. maurizio.casarin@unipd.it silvia.carlotto@unipd.it.
authors.forename: F
authors.initials: F
authors.lastname: Sedona
authors.affiliation: Istituto di Chimica della Materia Condensata e di Tecnologie per l'Energia - ICMATE, Via Francesco Marzolo 1, 35131 Padova, Italy.
authors.forename: A
authors.identifier: http://orcid.org/0000-0003-3733-9166
authors.initials: A
authors.lastname: Vittadini
authors.affiliation: Instituto de Ciencia de Materiales de Aragón and Departamento de Física de la Materia Condensada, Universidad de Zaragoza - CSIC, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Bartolomé
authors.affiliation: Instituto de Ciencia de Materiales de Aragón and Departamento de Física de la Materia Condensada, Universidad de Zaragoza - CSIC, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
authors.forename: F
authors.initials: F
authors.lastname: Bartolomé
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Francesco Marzolo 1, 35131 Padova, Italy. maurizio.casarin@unipd.it silvia.carlotto@unipd.it and Istituto di Chimica della Materia Condensata e di Tecnologie per l'Energia - ICMATE, Via Francesco Marzolo 1, 35131 Padova, Italy.
authors.forename: M
authors.initials: M
authors.lastname: Casarin