Density-functional theory models of Fe(iv)O reactivity in metal–organic frameworks: self-interaction error, spin delocalisation and the role of hybrid exchange
Literature Information
Fernan Saiz, Leonardo Bernasconi
We study the reactivity of Fe(IV)O moieties supported by a metal–organic framework (MOF-74) in the oxidation reaction of methane to methanol using all-electron, periodic density-functional theory calculations. We compare results concerning the electronic properties and reactivity obtained using two hybrid (B3LYP and sc-BLYP) and two standard generalised gradient corrected (PBE and BLYP) semi-local density functional approximations. The semi-local functionals are unable to reproduce the expected reaction profiles and yield a qualitatively incorrect representation of the reactivity. Non-local hybrid functionals provide a substantially more reliable description and predict relatively modest (ca. 60 kJ mol−1) reaction energy barriers for the H-atom abstraction reaction from CH4 molecules. We examine the origin of these differences and we highlight potential means to overcome the limitations of standard semi-local functionals in reactivity calculations in solid-state systems.
Related Literature
Formal total synthesis of (−)-haouamine A‡
Alois Fürstner, Jens Ackerstaff
DOI: 10.1039/B805295F
Hysteretic sorption of light gases by a porous metal–organic framework containing tris(para-carboxylated) triphenylphosphine oxide‡
Shaunt E. Oungoulian, Ji Woong Yoon, Young Kyu Hwang, Erica R. Wise, Jong-San Chang
DOI: 10.1039/B802809E
One-step preparation of positively-charged gold nanoraspberry
Hiroshi Shiigi, Yojiro Yamamoto, Naonobu Yoshi, Hidenobu Nakao, Tsutomu Nagaoka
DOI: 10.1039/B610085F
Selective monitoring of parts per million levels of CO by covalently immobilized metal complexes on glass
Tarkeshwar Gupta, Marc Altman, Sandra Lo Schiavo, Placido G. Mineo, Ignazio L. Fragalà, Guennadi Evmenenko, Pulak Dutta, Milko E. van der Boom
DOI: 10.1039/B802670J
Efficient visible light-active N-doped TiO2 photocatalysts by a reproducible and controllable synthetic route
Suil In, Alexander Orlov, Felipe García, Mintcho Tikhov, Dominic S. Wright, Richard M. Lambert
DOI: 10.1039/B610316B
Thermoreversible sol–gel transition of an aqueous solution of polyrotaxane composed of highly methylated α-cyclodextrin and polyethylene glycol
Masatoshi Kidowaki, Toshiyuki Kataoka
DOI: 10.1039/B607373E
Highly fluorescent supramolecular gels with chirality transcription through hydrogen bonding
Jangwon Seo, Jong Won Chung, Eun-Hye Jo, Soo Young Park
DOI: 10.1039/B802096E
Solvents for ring-closing metathesis reactions
Claire S. Adjiman, Adam J. Clarke, Gregory Cooper, Paul C. Taylor
DOI: 10.1039/B802921K
You might also like
What are the main uses of 4-Nitrophenyl phosphate disodium salt hexahydrate (CAS: 333338-18-4)?
4-Nitrophenyl phosphate disodium salt hexahydrate is primarily used as a substra...
What are the main uses of 2-(Trifluoromethyl)-1,3-oxazole-4-carboxylic Acid (CAS: 1060816-01-4)?
2-(Trifluoromethyl)-1,3-oxazole-4-carboxylic Acid (CAS: 1060816-01-4) is widely ...
How should 2-Fluoro-4-biphenylcarboxylic acid (CAS: 137045-30-8) be stored?
2-Fluoro-4-biphenylcarboxylic acid should be stored in a cool, dry place at room...
What industries use Prednisolone-21-Carboxylic Acid (CAS: 61549-70-0)?
Prednisolone-21-Carboxylic Acid is primarily used in the pharmaceutical industry...
How should 4-(Hydrazinomethyl)-1,2,3-benzenetriol (CAS: 3614-72-0) be stored?
4-(Hydrazinomethyl)-1,2,3-benzenetriol (CAS: 3614-72-0) should be stored in a co...
What industries use 4-Amino-1-methyl-1H-pyrazole-5-carboxylic acid hydrochloride (CAS: 92534-70-8)?
4-Amino-1-methyl-1H-pyrazole-5-carboxylic acid hydrochloride (CAS: 92534-70-8) i...
What regulatory guidelines apply to dehydropachymic acid (CAS: 77012-31-8)?
Dehydropachymic acid (CAS: 77012-31-8) is regulated by various agencies. It fall...
What is the market or research trend for 6-[(2,2-Dimethylpropanoyl)amino]nicotinic acid (CAS: 898561-66-5)?
The market and research trends for 6-[(2,2-Dimethylpropanoyl)amino]nicotinic aci...
How should 1,10-Phenanthroline-2,9-dicarbaldehyde (CAS: 57709-62-3) be stored?
1,10-Phenanthroline-2,9-dicarbaldehyde should be stored in a cool, dry place awa...
How is 5-Carbamoyl-11-oxo-10,11-dihydro-5H-dibenzo[b,f]azepin-10-yl acetate (CAS: 113952-21-9) typically synthesized?
5-Carbamoyl-11-oxo-10,11-dihydro-5H-dibenzo[b,f]azepin-10-yl acetate can be synt...
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.










![1-[(4-Methylphenyl)sulfonyl]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine-5-carbonitrile structure 1-[(4-Methylphenyl)sulfonyl]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine-5-carbonitrile structure](https://static.chemtradehub.com/structs/143/1434747-57-5-fc0d.webp)



