期刊
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
卷 10, 期 5, 页码 1934-1952出版社
AMER CHEMICAL SOC
DOI: 10.1021/ct400956h
关键词
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资金
- Austrian Academy of Sciences
- Adams fellowship of the Israel Academy of Sciences and Humanities
- European Research Council
- Israel Science Foundation
- United States-Israel Binational Science Foundation
- Germany-Israel Foundation
- Wolfson Foundation
- Hemlsley Foundation
- Austrian Science Fund (FWF) [P24666-N20]
- German Science Foundation [DFG/GRK 1640]
- Molecular Foundry
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering (Theory FWP) [DE-AC02-05CH11231]
- Scientific Discovery through Advanced Computing (SciDAC) Partnership program - U.S. Department of Energy, Office of Science, Advanced Scientific Computing Research and Basic Energy Sciences
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy
- Austrian Science Fund (FWF) [P24666] Funding Source: Austrian Science Fund (FWF)
Density functional theory with optimally tuned range-separated hybrid (OT-RSH) functionals has been recently suggested [Refaely-Abramson et al. Phys. Rev. Lett. 2012, 109, 226405] as a nonempirical approach to predict the outer-valence electronic structure of molecules with the same accuracy as many-body perturbation theory. Here, we provide a quantitative evaluation of the OT-RSH approach by examining its performance in predicting the outer-valence electron spectra of several prototypical gas-phase molecules, from aromatic rings (benzene, pyridine, and pyrimidine) to more complex organic systems (terpyrimidinethiol and copper phthalocyanine). For a range up to several electronvolts away from the frontier orbital energies, we find that the outer-valence electronic structure obtained from the OT-RSH method agrees very well (typically within similar to 0.1-0.2 eV) with both experimental photoemission and theoretical many-body perturbation theory data in the GW approximation. In particular, we find that with new strategies for an optimal choice of the short-range fraction of Fock exchange, the OT-RSH approach offers a balanced description of localized and delocalized states. We discuss in detail the sole exception found-a high-symmetry orbital, particular to small aromatic rings, which is relatively deep inside the valence state manifold. Overall, the OT-RSH method is an accurate DFT-based method for outer-valence electronic structure prediction for such systems and is of essentially the same level of accuracy as contemporary GW approaches, at a reduced computational cost.
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