No need for external orthogonality in subsystem density-functional theory
Literature Information
Jan P. Unsleber, Johannes Neugebauer, Christoph R. Jacob
Recent reports on the necessity of using externally orthogonal orbitals in subsystem density-functional theory (SDFT) [Annu. Rep. Comput. Chem., 8, 2012, 53; J. Phys. Chem. A, 118, 2014, 9182] are re-investigated. We show that in the basis-set limit, supermolecular Kohn–Sham-DFT (KS-DFT) densities can exactly be represented as a sum of subsystem densities, even if the subsystem orbitals are not externally orthogonal. This is illustrated using both an analytical example and in basis-set free numerical calculations for an atomic test case. We further show that even with finite basis sets, SDFT calculations using accurate reconstructed potentials can closely approach the supermolecular KS-DFT density, and that the deviations between SDFT and KS-DFT decrease as the basis-set limit is approached. Our results demonstrate that formally, there is no need to enforce external orthogonality in SDFT, even though this might be a useful strategy when developing projection-based DFT embedding schemes.
Related Literature
From cellulose fibrils to single chains: understanding cellulose dissolution in ionic liquids
Xueming Yuan, Gang Cheng
DOI: 10.1039/C5CP05744B
Solvent transport through hard–soft segmented polymer nanocomposites
Sangram K. Rath, Saji S. Edatholath, T. Umasankar Patro, Kathi Sudarshan, P. U. Sastry, Pradeep K. Pujari, G. Harikrishnan
DOI: 10.1039/C5CP04432D
Singular analysis and coupled cluster theory
Heinz-Jürgen Flad, Gohar Harutyunyan, Bert-Wolfgang Schulze
DOI: 10.1039/C5CP01183C
A slowing down of proton motion from HPTS to water adsorbed on the MCM-41 surface
Noemí Alarcos, Boiko Cohen, Abderrazzak Douhal
DOI: 10.1039/C5CP04548G
Mixtures of the 1-ethyl-3-methylimidazolium acetate ionic liquid with different inorganic salts: insights into their interactions
Filipe S. Oliveira, Eurico J. Cabrita, Smilja Todorovic, Carlos E. S. Bernardes, Jennifer L. Hodgson, Douglas R. MacFarlane, Luís P. N. Rebelo, Isabel M. Marrucho
DOI: 10.1039/C5CP06937H
Variable electronic properties of lateral phosphorene–graphene heterostructures
Xiaoqing Tian, Lin Liu, Yu Du, Juan Gu, Jian-bin Xu, Boris I. Yakobson
DOI: 10.1039/C5CP05443E
Defect chemistry and lithium transport in Li3OCl anti-perovskite superionic conductors
Chi Chen, Zarah Medina Baiyee, Xin Chen, Chunming Niu
DOI: 10.1039/C5CP05722A
Probing the effects of 2D confinement on hydrogen dynamics in water and ice adsorbed in graphene oxide sponges
Giovanni Romanelli, Xuan Zhang, Kian Ping Loh, Carla Andreani
DOI: 10.1039/C5CP05240H
High resolution absolute absorption cross sections of the 1A′–1A′ transition of the CH2OO biradical
Elizabeth S. Foreman, Kara M. Kapnas, YiTien Jou, Jarosław Kalinowski, David Feng, Craig Murray
DOI: 10.1039/C5CP04977F
You might also like
How should waste containing (6-Bromo-2-naphthyl)oxy](dimethyl)(2-methyl-2-propanyl)silane be handled?
Waste containing (6-Bromo-2-naphthyl)oxy](dimethyl)(2-methyl-2-propanyl)silane (...
How is 7-Fluoro-4-isoquinolinecarboxylic acid (CAS: 1841081-40-0) typically synthesized?
7-Fluoro-4-isoquinolinecarboxylic acid can be synthesized via a multi-step proce...
What are the physical and chemical properties of 2,3,5,6-Tetrabromothieno[3,2-b]thiophene (CAS: 124638-53-5)?
2,3,5,6-Tetrabromothieno[3,2-b]thiophene is a crystalline compound with a high m...
Is 1-[4-(Benzylamino)-7,8-dihydro-5H-pyrano[4,3-d]pyrimidin-2-yl]-2-methyl-1H-indole-4-carboxamide (CAS: 1542705-92-9) safe?
1-[4-(Benzylamino)-7,8-dihydro-5H-pyrano[4,3-d]pyrimidin-2-yl]-2-methyl-1H-indol...
What is the market or research trend for imidazo[5,1-d]-1,2,3,5-tetrazine-8-carboxylic acid, 3,4-dihydro-3-methyl-4-oxo- (CAS: 113942-30-6)?
The market for imidazo[5,1-d]-1,2,3,5-tetrazine-8-carboxylic acid, 3,4-dihydro-3...
What is 3-(Triisopropylsilyl)propiolaldehyde (CAS: 163271-80-5)?
3-(Triisopropylsilyl)propiolaldehyde is a synthetic organic compound with the CA...
What regulatory guidelines apply to 6-Nitro-2H-1,4-benzoxazin-3(4H)-one (CAS: 81721-87-1)?
6-Nitro-2H-1,4-benzoxazin-3(4H)-one (CAS: 81721-87-1) is subject to various regu...
How should waste containing (3-Fluorophenyl)(4-{[(2-methyl-2-propanyl)oxy]carbonyl}-1-piperazinyl)acetic acid (CAS: 885272-91-3) be handled?
Waste containing (3-Fluorophenyl)(4-{[(2-methyl-2-propanyl)oxy]carbonyl}-1-piper...
What are the physical and chemical properties of N,N'-4,4'-Biphenyldiyldiisonicotinamide (CAS: 55119-40-9)?
N,N'-4,4'-Biphenyldiyldiisonicotinamide is a white crystalline solid with a mole...
What industries use 6-Bromo-8-fluoro-2-quinazolinol (CAS: 1036756-15-6)?
6-Bromo-8-fluoro-2-quinazolinol is primarily used in the pharmaceutical industry...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














![Sodium 3-[(E)-(4-anilinophenyl)diazenyl]benzenesulfonate structure Sodium 3-[(E)-(4-anilinophenyl)diazenyl]benzenesulfonate structure](https://static.chemtradehub.com/structs/587/587-98-4-035f.webp)