Coverage dependence of the level alignment for methanol on TiO2(110)

Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. We perform calculations to determine the coverage dependence of the level alignment for a prototypical photocatalyti...

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Detalles Bibliográficos
Autores: Migani, Annapaola|||0000-0001-5422-805X, Mowbray, Duncan J.|||0000-0002-8520-0364
Tipo de recurso: artículo
Fecha de publicación:2014
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:212915
Acceso en línea:https://ddd.uab.cat/record/212915
https://dx.doi.org/urn:doi:10.1016/j.comptc.2014.03.007
Access Level:acceso abierto
Palabra clave:HOMO
Level alignment
Photocatalysis
Two photon photoemission
Ultraviolet photoemission spectroscopy
Wet electron level
Descripción
Sumario:Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. We perform calculations to determine the coverage dependence of the level alignment for a prototypical photocatalytic interface: 12 and 1 monolayer (ML) intact and dissociated CHOH on rutile TiO(110). We find changes in the wavefunction's spatial distribution, and a consequent renormalization of the quasiparticle energy levels, as a function of CHOH coverage and dissociation. Our results suggest that the occupied molecular levels responsible for hole trapping are not those observed in the ultraviolet photoemission spectroscopy (UPS) spectrum. Rather, they are those of isolated CHO on the surface. We find the unoccupied molecular levels have either 2D character with weight above the surface at 1 ML coverage, or significant hybridization with the surface at 12 ML coverage. These results suggest the resonance observed in the two photon phooemission (2PP) spectrum arises from excitations to unoccupied "Wet electron" levels with 2D character.