Solid state effects on the electronic structure of H sub(2)OEP

• Published in: Physical chemistry chemical physics : PCCP Vol. 16; no. 48; pp. 27104 - 27111
• Main Authors: Marsili, M, Umari, P, Di Santo, G, Caputo, M, Panighel, M, Goldoni, A, Kumar, M, Pedio, M
• Format: Journal Article
• Language: English
• Published: 01.11.2014
• Subjects: Deposition; Electronic structure; Electronics; Gas phases; Mathematical analysis; Molecular orbitals; Photoemission; Reduction
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c4cp03450c

We present the results of a joint experimental and theoretical investigation concerning the effect of crystal packing on the electronic properties of the H sub(2)OEP molecule. Thin films, deposited in ultra high vacuum on metal surfaces, are investigated by combining valence band photoemission, inverse photoemission, and X-ray absorption spectroscopy. The spectra of the films are compared, when possible, with those measured in the gas phase. Once many-body effects are included in the calculations through the GW method, the electronic structure of H sub(2)OEP in the film and gas phase are accurately reproduced for both valence and conduction states. Upon going from an isolated molecule to the film phase, the electronic gap shrinks significantly and the lowest unoccupied molecular orbital (LUMO) and LUMO + 1 degeneracy is removed. The calculations show that the reduction of the transport gap in the film is entirely addressable to the enhancement of the electronic screening.