Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 10, Issue 5, Pages 2103-2113Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ct500087v
Keywords
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Funding
- European Projects DYNamo [ERC-2010-AdG-267374]
- CRONOS [280879-2]
- Grupos Consolidados UPV/EHU del Gobierno Vasco [IT-319-07]
- NSFC [21003113, 21121003]
- MOST [2011CB921404]
- NSF [CHE-1213189]
- [FIS2012-37549-C05-02]
- [FIS2010-21282-C02-01]
- [PIB2010US-00652]
- [RYC-2011-09582]
- [JCI-2010-08156]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1213189] Funding Source: National Science Foundation
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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 TiO2(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 G(0)W(0), scQPGW1, scQPGW(0), and scQPGW QP calculations. Our results demonstrate that G0W0, 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.
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