Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems
Abstract
The accurate prediction of electronic and optical properties of molecules and solids is a persistent challenge for methods based on density functional theory. We propose a generalization of dielectric-dependent hybrid functionals to finite systems where the definition of the mixing fraction of exact and semilocal exchange is physically motivated, nonempirical, and system dependent. The proposed functional yields ionization potentials, and fundamental and optical gaps of many, diverse molecular systems in excellent agreement with experiments, including organic and inorganic molecules and semiconducting nanocrystals. As a result, we further demonstrate that this hybrid functional gives the correct alignment between energy levels of the exemplary TTF-TCNQ donor-acceptor system.
- Authors:
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1328479
- Alternate Identifier(s):
- OSTI ID: 1335882
- Grant/Contract Number:
- AC02-06CH11357; AC02-05CH11231; AC52-06NA25396
- Resource Type:
- Published Article
- Journal Name:
- Physical Review. X
- Additional Journal Information:
- Journal Name: Physical Review. X Journal Volume: 6 Journal Issue: 4; Journal ID: ISSN 2160-3308
- Publisher:
- American Physical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS
Citation Formats
Brawand, Nicholas P., Vörös, Márton, Govoni, Marco, and Galli, Giulia. Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems. United States: N. p., 2016.
Web. doi:10.1103/PhysRevX.6.041002.
Brawand, Nicholas P., Vörös, Márton, Govoni, Marco, & Galli, Giulia. Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems. United States. https://doi.org/10.1103/PhysRevX.6.041002
Brawand, Nicholas P., Vörös, Márton, Govoni, Marco, and Galli, Giulia. Tue .
"Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems". United States. https://doi.org/10.1103/PhysRevX.6.041002.
@article{osti_1328479,
title = {Generalization of Dielectric-Dependent Hybrid Functionals to Finite Systems},
author = {Brawand, Nicholas P. and Vörös, Márton and Govoni, Marco and Galli, Giulia},
abstractNote = {The accurate prediction of electronic and optical properties of molecules and solids is a persistent challenge for methods based on density functional theory. We propose a generalization of dielectric-dependent hybrid functionals to finite systems where the definition of the mixing fraction of exact and semilocal exchange is physically motivated, nonempirical, and system dependent. The proposed functional yields ionization potentials, and fundamental and optical gaps of many, diverse molecular systems in excellent agreement with experiments, including organic and inorganic molecules and semiconducting nanocrystals. As a result, we further demonstrate that this hybrid functional gives the correct alignment between energy levels of the exemplary TTF-TCNQ donor-acceptor system.},
doi = {10.1103/PhysRevX.6.041002},
journal = {Physical Review. X},
number = 4,
volume = 6,
place = {United States},
year = {Tue Oct 04 00:00:00 EDT 2016},
month = {Tue Oct 04 00:00:00 EDT 2016}
}
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https://doi.org/10.1103/PhysRevX.6.041002
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