L-2,L-3-edges absorption spectra of FePc (I) and FePc(eta(2)-O-2) (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 L-I/II(3) intensity 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 L-I/II(3) higher EE side. The occurrence of states involving metal to ligand charge transfer transitions implying low lying empty pi* ligand-based orbitals on the L-I/II(3) higher EE sides have been confirmed.

L2,3-edges absorption spectra of a 2D complex system: a theoretical modelling

CARLOTTO, SILVIA;SAMBI, MAURO;SEDONA, FRANCESCO;VITTADINI, ANDREA;CASARIN, MAURIZIO
2016

Abstract

L-2,L-3-edges absorption spectra of FePc (I) and FePc(eta(2)-O-2) (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 L-I/II(3) intensity 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 L-I/II(3) higher EE side. The occurrence of states involving metal to ligand charge transfer transitions implying low lying empty pi* ligand-based orbitals on the L-I/II(3) higher EE sides have been confirmed.
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/3211228
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 16
  • ???jsp.display-item.citation.isi??? 16
  • OpenAlex ND
social impact