Fractional electron number, temperature, and perturbations in chemical reactions
Literature Information
Paul W. Ayers
We provide a perspective on the role of non-integer electron number in the density functional theory approach to chemical reactivity (conceptual DFT), emphasizing that it is important to not only treat reagents as open systems, but also as non-isolated systems, in contact with their surroundings. The special case of well-separated reagents is treated in some detail, as is the case where reagents interact strongly. The resulting expressions for the chemical potential of an acid, μacid = −(αI + A)/(1 + α), and a base, μbase = −(I + αA)/(1 + α), elucidate and generalize the assumptions inherent in the chemical potential models of Mulliken (α = 1) and Gazquez, Cedillo, and Vela (α = 3). In the strongly-interacting limit, it is appropriate to model the effects of the environment as a state-specific effective temperature, thereby providing a rigorous justification for the phenomenological effective-temperature model one of the authors previously proposed. The framework for the strongly interacting limit subsumes our model for weakly-interacting subsystems at nonzero temperature, the case of open but otherwise noninteracting subsystems, and the zero-temperature limit.
Recommended Journals
Related Literature
Pictet–Spengler reaction based on in situ generated α-amino iminium ions through the Heyns rearrangement
Guo-bin Yang, Yong-po Zhang, Dong-dong Guo, Jin-zhong Zhao, Guang-xun Li, Zhuo Tang
DOI: 10.1039/D0QO00722F
Organoselenium chemistry-based polymer synthesis
Qilong Li, Yuanyuan Zhang, Zijun Chen, Xiangqiang Pan, Zhengbiao Zhang, Jian Zhu
DOI: 10.1039/D0QO00640H
Correction: Hydride transfer enabled switchable dearomatization of indoles in the carbocyclic ring and the pyrrole ring
Kang Duan, Hongjin Shi, Lin-Xuan Wang, Shuai-Shuai Li, Lubin Xu
DOI: 10.1039/D0QO90064H
The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles‡
Lin-Sheng Lei, Cao-Gen Xue, Xue-Tao Xu, Da-Ping Jin, Wen Bao, Huan Liang, Kun Zhang, Abdullah M. Asiri
DOI: 10.1039/C9OB00510B
Acid–base controlled multiple conformation and aromaticity switches in tren-capped hexaphyrins
Stéphane Le Gac, Elsa Caytan, Vincent Dorcet, Bernard Boitrel
DOI: 10.1039/C9OB00489K
Recent advances in the synthesis of xanthones and azaxanthones
DOI: 10.1039/D0QO00659A
Catalytic asymmetric cycloaddition reactions of enoldiazo compounds
Kostiantyn O. Marichev, Michael P. Doyle
DOI: 10.1039/C9OB00478E
Recent advances in the asymmetric synthesis of pharmacology-relevant nitrogen heterocycles via stereoselective aza-Michael reactions
Maxim G. Vinogradov, Olga V. Turova, Sergei G. Zlotin
DOI: 10.1039/C8OB03034K
A cell-permeant small molecule for the super-resolution imaging of the endoplasmic reticulum in live cells
Adiki Raja Sekhar, Bhagaban Mallik, Vimlesh Kumar, Jeyaraman Sankar
DOI: 10.1039/C9OB00408D
Oxidative oxy-cyclization of 2-alkynylbenzamide enabled by TBAB/Oxone: switchable synthesis of isocoumarin-1-imines and isobenzofuran-1-imine
Guanyinsheng Qiu, Hongwei Zhou, Jin-Biao Liu
DOI: 10.1039/C9OB00320G
You might also like
Is 2-(2-chloroacetamido)-3-phenylpropanoic acid (CAS: 7765-11-9) safe?
2-(2-Chloroacetamido)-3-phenylpropanoic acid (CAS: 7765-11-9) is generally consi...
Is 2-(Benzyloxy)-5-bromobenzoic acid (CAS: 62176-31-2) safe?
2-(Benzyloxy)-5-bromobenzoic acid can be handled safely if appropriate precautio...
What is (4-Methyl-1,2,5-oxadiazol-3-yl)methanamine hydrochloride (CAS: 1159825-48-5)?
(4-Methyl-1,2,5-oxadiazol-3-yl)methanamine hydrochloride is a chemical compound ...
What is 2-(5-Hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS: 917985-54-7)?
2-(5-Hexylthiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS: 917985-54...
Are there alternatives to 4-(8-Methyl-9H-1,3-dioxolo[4,5-h][2,3]benzodiazepin-5-yl)benzenamine (CAS: 102771-26-6) in synthesis?
While 4-(8-Methyl-9H-1,3-dioxolo[4,5-h][2,3]benzodiazepin-5-yl)benzenamine (CAS:...
What is the market or research trend for tert-butyl 3-hydroxy-4,5,7,8-tetrahydro-2H-pyrazolo[3,4-d]azepine-6-carboxylate (CAS: 851376-80-2)?
The market for tert-butyl 3-hydroxy-4,5,7,8-tetrahydro-2H-pyrazolo[3,4-d]azepine...
How should waste containing 3,5-Diamino-1H-pyrazole-4-carbonitrile (CAS: 6844-58-2) be handled?
Waste containing 3,5-Diamino-1H-pyrazole-4-carbonitrile (CAS: 6844-58-2) should ...
How is (6-Fluoro-3-pyridinyl)boronic acid (CAS: 351019-18-6) typically synthesized?
(6-Fluoro-3-pyridinyl)boronic acid can be synthesized through the reaction of 6-...
What industries use Dibenzyl carbonimidoylbiscarbamate (CAS: 10065-79-9)?
Dibenzyl carbonimidoylbiscarbamate (CAS: 10065-79-9) finds applications in vario...
What is the market or research trend for (beta,beta,2,3,4,5,6-~2~H_7_)Phenylalanine (CAS: 74228-83-4)?
The market for (beta,beta,2,3,4,5,6-~2~H_7_)Phenylalanine (CAS: 74228-83-4) is g...
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.










![(1R)-N-((1R)-1-Phenylethyl)-1-[4-(tert-butyldimethylsilyloxymethyl)cyclohexyl]ethan-1-amine structure (1R)-N-((1R)-1-Phenylethyl)-1-[4-(tert-butyldimethylsilyloxymethyl)cyclohexyl]ethan-1-amine structure](https://static.chemtradehub.com/structs/672/672314-45-3-47ef.webp)

![2-[(E)-(2-Methoxyphenyl)diazenyl]-3-oxo-N-(2-oxo-2,3-dihydro-1H-benzimidazol-5-yl)butanamide structure 2-[(E)-(2-Methoxyphenyl)diazenyl]-3-oxo-N-(2-oxo-2,3-dihydro-1H-benzimidazol-5-yl)butanamide structure](https://static.chemtradehub.com/structs/821/82199-12-0-f1d0.webp)

