Quasiparticle level alignment for photocatalytic interfaces
Migani, Annapaola (Institut Català de Nanociència i Nanotecnologia)
Mowbray, Duncan J. (Universidad del País Vasco. Departamento de Física de Materiales)
Zhao, Jin (University of Science and Technology of China)
Petek, Hrvoje (University of Pittsburgh. Department of Physics and Astronomy)
Rubio, Ángel (Universidad del País Vasco. Departamento de Física de Materiales)

Data:	2014
Resum:	Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. Standard density functional theory (DFT)-based methods have proven unable to provide a quantitative description of this level alignment. This requires a proper treatment of the anisotropic screening, necessitating the use of quasiparticle (QP) techniques. However, the computational complexity of QP algorithms has meant a quantitative description of interfacial levels has remained elusive. We provide a systematic study of a prototypical interface, bare and methanol-covered rutile TiO(110) surfaces, to determine the type of many-body theory required to obtain an accurate description of the level alignment. This is accomplished via a direct comparison with metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), and two-photon photoemission (2PP) spectroscopy. We consider GGA DFT, hybrid DFT, and GW, scQPGW1, scQPGW, and scQPGW QP calculations. Our results demonstrate that GW, or our recently introduced scQPGW1 approach, are required to obtain the correct alignment of both the highest occupied and lowest unoccupied interfacial molecular levels (HOMO/LUMO). These calculations set a new standard in the interpretation of electronic structure probe experiments of complex organic molecule/semiconductor interfaces.
Ajuts:	European Commission 267374 European Commission 280879 Ministerio de Economía y Competitividad FIS2012-37549-C05-02 Ministerio de Economía y Competitividad FIS2010-21282-C02-01 Ministerio de Economía y Competitividad PIB2010US-00652 Ministerio de Economía y Competitividad RYC-2011-09582 Ministerio de Economía y Competitividad JCI-2010-08156
Drets:	Tots els drets reservats.
Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Publicat a:	Journal of chemical theory and computation, Vol. 10, Issue 5 (May 2014) , p. 2103-2113, ISSN 1549-9626

DOI: 10.1021/ct500087v

Postprint 11 p, 1.4 MB

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