Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(vi) hydroxide in aqueous solution
Literature Information
Xia Yang, Dongqi Wang
Four types of reaction mechanisms for the oxo ligand exchange of monomeric and dimeric neptunyl(VI) hydroxide in aqueous solution were explored computationally using density functional theory (DFT) and ab initio classical molecular dynamics. The obtained results were compared with previous studies on the oxo exchange of uranyl hydroxide, as well as with experiments. It is found that the stable T-shaped [NpO3(OH)3]3− intermediate is a key species for oxo exchange in the proton transfer in mononuclear Path I and binuclear Path IV, similar to the case of uranyl(VI) hydroxide. Path I is thought to be the preferred oxo exchange mechanism for neptunyl(VI) hydroxide in our calculations, due to the lower activation energy (22.7 and 13.1 kcal mol−1 for ΔG‡ and ΔH‡, respectively) of the overall reaction. Path II via a cis-neptunyl structure assisted by a water molecule might be a competitive channel against Path I with a mononuclear mechanism, owing to a rapid dynamical process occurring in Path II. In Path IV with the binuclear mechanism, oxo exchange is accomplished via the interaction between [NpO2(OH)4]2− and T-shaped [NpO3(OH)3]3− with a low activation energy for the rate-determining step, however, the overall energy required to fulfill the reaction is slightly higher than that in mononuclear Path I, suggesting a possible binuclear process in the higher energy region. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).
Recommended Journals
Related Literature
Nanoscopic structures and molecular interactions leading to a dystectic and two eutectic points in [EMIm][Cl]/urea mixtures
Ulrike Cerajewski, Jennica Träger, Selgar Henkel, Andreas H. Roos, Martin Brehm, Dariush Hinderberger
DOI: 10.1039/C8CP04912B
The structural and electronic properties of 3,3′-azothiophene photo-switching systems
Patrick R. Huddleston, Victor V. Volkov, Carole C. Perry
DOI: 10.1039/C8CP06059B
Tuning core–shell interactions in tungsten carbide–Pt nanoparticles for the hydrogen evolution reaction
Akash Jain, Ashwin Ramasubramaniam
DOI: 10.1039/C8CP04113J
Size, dimensionality and composition effects on the Debye temperature of nanocrystals
Yan-Li Ma, Ke Zhu, Ming Li
DOI: 10.1039/C8CP04935A
Fullerene and endometallofullerene Kagome lattices with symmetry-forced spin frustration
Dmitri V. Konarev, Salavat S. Khasanov, Yasuhiro Shimizu, Alexey V. Kuzmin, Rimma N. Lyubovskaya
DOI: 10.1039/C8CP07017B
Distinctive phase separation dynamics of polymer blends: roles of Janus nanoparticles
Qing Li, Liquan Wang, Jiaping Lin, Liangshun Zhang
DOI: 10.1039/C8CP06431H
Influence of humidity and iron(iii) on photodegradation of atmospheric secondary organic aerosol particles
Kurtis T. Malecha, Markus Ammann, Sergey A. Nizkorodov
DOI: 10.1039/C8CP03981J
Correlation between the magnetic-microstructure and microwave mitigation ability of MxCo(1−x)Fe2O4 based ferrite–carbon black/PVA composites
Chetan Kotabage, Suwarna Datar, Ashutosh C. Abhyankar
DOI: 10.1039/C8CP05235B
You might also like
How should waste containing 4-Bromo-3-methyl-2-thiophenecarboxylic acid (CAS: 265652-39-9) be handled?
Waste containing 4-Bromo-3-methyl-2-thiophenecarboxylic acid (CAS: 265652-39-9) ...
What industries use (2S,5S,2'S,5'S)-1,1'-(1,2-Ethanediyl)bis(2,5-dimethylphospholane) (CAS: 136779-26-5)?
(2S,5S,2'S,5'S)-1,1'-(1,2-Ethanediyl)bis(2,5-dimethylphospholane) is primarily u...
What industries use Ethyl 2-(2-bromo-5-fluorophenyl)acetate (CAS: 1214910-61-8)?
Ethyl 2-(2-bromo-5-fluorophenyl)acetate (CAS: 1214910-61-8) is used in the pharm...
How is 4-Methyl-2-benzofuran-1,3-dione (CAS: 4792-30-7) typically synthesized?
4-Methyl-2-benzofuran-1,3-dione (CAS: 4792-30-7) can be synthesized through seve...
What industries use 4,6-Dichloroquinoline-3-carbonitrile (CAS: 936498-04-3)?
4,6-Dichloroquinoline-3-carbonitrile (CAS: 936498-04-3) is used in the pharmaceu...
What are the main uses of Chloro[tris(para-trifluoromethylphenyl)phosphine]gold(I) (CAS: 385815-83-8)?
Chloro[tris(para-trifluoromethylphenyl)phosphine]gold(I) is primarily used in or...
Is 2-Bromo-5-nitrofuran (CAS: 823-73-4) safe?
2-Bromo-5-nitrofuran (CAS: 823-73-4) is generally considered safe when handled w...
How should 5-Bromo-2,3,4-trifluorobenzoic acid (CAS: 212631-85-1) be stored?
5-Bromo-2,3,4-trifluorobenzoic acid should be stored in a cool, dry place away f...
What are the main uses of Zinc bis(aminoacetate) (CAS: 7214-08-6)?
Zinc bis(aminoacetate) (CAS: 7214-08-6) is primarily used in the pharmaceutical ...
How should Adamantan-1-ylmethanol (CAS: 770-71-8) be stored?
Adamantan-1-ylmethanol should be stored in a cool, dry, and well-ventilated plac...
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.











![(2S)-{[(9H-Fluoren-9-ylmethoxy)carbonyl]amino}(phenyl)acetic acid structure (2S)-{[(9H-Fluoren-9-ylmethoxy)carbonyl]amino}(phenyl)acetic acid structure](https://static.chemtradehub.com/structs/102/102410-65-1-4aa7.webp)

![[4-(Hydroxymethyl)phenyl]acetic acid structure [4-(Hydroxymethyl)phenyl]acetic acid structure](https://static.chemtradehub.com/structs/734/73401-74-8-5a54.webp)
