Ultra-fast charge migration competes with proton transfer in the early chemistry of H2O˙+
文献信息
Furong Wang, Uli Schmidhammer, Aurélien de La Lande, Mehran Mostafavi
Oxidation by the ultra-short lived radical cation of water, H2O˙+, can potentially take place at the interface of water and numerous heterogeneous systems involved in radiation therapy, energy and environmental industries. The oxidation processes induced by H2O˙+ can be mimicked in highly concentrated solutions where the nearest neighbors of H2O˙+ may be molecules other than water. The reactivity of H2O˙+ and D2O˙+ is probed in hydrogenated and deuterated sulfuric acid solutions of various concentrations. The oxidized solute, sulfate radical, is observed at 7 ps and remarkably higher yields are found in deuterated solutions. The isotopic effects reveal the competition between two ultrafast reactions: proton transfer toward H2O (D2O) and electron transfer from HSO4− to H2O˙+ (D2O˙+). Density functional theory simulations decipher the electron transfer mechanism: it proceeds via sub-femtosecond charge migration and is not affected by isotopic substitution. This work definitively demonstrates why direct oxidation triggered by H2O˙+ can be competitive with proton transfer.
相关文献
Distinctive electron transport on pyridine-linked molecular junctions with narrow monolayer graphene nanoribbon electrodes compared with metal electrodes and graphene electrodes
Jie Li, Tao Li, Yi Zhou, Weikang Wu, Leining Zhang, Hui Li
DOI: 10.1039/C6CP05007G
Direct photoisomerization of CH2I2vs. CHBr3 in the gas phase: a joint 50 fs experimental and multireference resonance-theoretical study
Veniamin A. Borin, Sergey M. Matveev, Darya S. Budkina, Patrick Z. El-Khoury, Alexander N. Tarnovsky
DOI: 10.1039/C6CP05129D
Ligand effects on the optical and chiroptical properties of the thiolated Au18 cluster
DOI: 10.1039/C6CP04298H
Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites
Aurélien M. A. Leguy, Jarvist M. Frost, Jonathan Skelton, Federico Brivio, Xabier Rodríguez-Martínez, Oliver J. Weber, Anuradha Pallipurath, M. Isabel Alonso, Mariano Campoy-Quiles, Mark T. Weller, Aron Walsh, Piers R. F. Barnes
DOI: 10.1039/C6CP03474H
N2 activation on Al metal clusters: catalyzing role of BN-doped graphene support
Deepak Kumar, Sourav Pal, Sailaja Krishnamurty
DOI: 10.1039/C6CP03342C
Isomerization of the methoxy radical revisited: the impact of water dimers
Pradeep Kumar, Partha Biswas, Biman Bandyopadhyay
DOI: 10.1039/C6CP04544H
Water desalination by electrical resonance inside carbon nanotubes
Jia-wei Feng, Hong-ming Ding
DOI: 10.1039/C6CP04201E
A detailed Raman and X-ray study of UO2+x oxides and related structure transitions
J. M. Elorrieta, L. J. Bonales, N. Rodríguez-Villagra, V. G. Baonza, J. Cobos
DOI: 10.1039/C6CP03800J
Prediction of flatness-driven quantum spin Hall effect in functionalized germanene and stanene
Run-wu Zhang, Wei-xiao Ji, Chang-wen Zhang, Ping Li, Pei-ji Wang
DOI: 10.1039/C6CP06216D
Hole-conductor-free perovskite solar cells with carbon counter electrodes based on ZnO nanorod arrays
B. X. Wang, T. F. Liu, Y. B. Zhou, X. Chen, X. B. Yuan, Y. Y. Yang, W. P. Liu, J. M. Wang, H. W. Han, Y. W. Tang
DOI: 10.1039/C6CP04793A
您可能还喜欢
什么是3-表南美楝属二醇(CAS号:19942-04-2)?
3-表南美楝属二醇是一种具有特定立体化学结构的化合物,其分子式为C31H52O2,属于甾醇类化合物。它具有光学活性,是一种复杂的有机分子,主要存在于一些植物中。
3-羧基-5-碘苯甲酸甲酯(CAS号:50765-22-5)应用于哪些行业?
3-羧基-5-碘苯甲酸甲酯主要应用于医药行业,作为合成某些药物中间体的重要原料。此外,它还可能用于聚合物的改性、传感器的制备以及半导体材料的制备等领域。
什么是3-Bromoindolin-2-one(CAS号:22942-87-6)?
3-Bromoindolin-2-one是一种含有溴代基团的吲哚酮衍生物,分子式为C9H7BrNO。它是一种无色固体,具有一定的挥发性,熔点为158-159°C...
如何处理含有L-Lysyl-L-phenylalanyl-L-isoleucylglycyl-L-leucyl-L-methioninamide(CAS号:2990-43-4)的废料?
对于含有该化合物的废液,应先进行中和处理,然后根据其毒性和活性选择合适的处置方法。可以考虑焚烧处理或由专业的化学品废物处理公司进行无害化处理。处理过程中需注意环...
ANGIOTENSIN 1/2 + A (2 - 8)(CAS号:51833-76-2)的物理化学性质是什么?
ANGIOTENSIN 1/2 + A (2 - 8)是一种蛋白质类化合物,具有典型的蛋白质性质。它的分子量约为5900 Da。该化合物在水中具有一定的溶解性,...
如何储存2-甲基硫代嘧啶-5-硼酸频那酯(CAS号:940284-18-4)?
应将该化合物存放在阴凉干燥、通风良好的地方,避免阳光直射。建议将化合物密封保存在避光的、干燥的容器中,远离火源和高温环境。
什么是苏丹红IV氘代物 标准品(CAS号:1014689-18-9)?
苏丹红IV氘代物 标准品是一种含有氘代标记的苏丹红IV化合物,是一种用于化合物分析、结构确证以及代谢研究的标准物质。
(+)-2-Amino-6-propionamido-d3-tetrahydrobenzothiazole(CAS号:1217680-69-7)适用哪些法规指南?
该化合物需要遵循《全球化学品统一分类和标签制度》(GHS)中的分类和标签要求,具体分类需依据其毒性和物理化学性质。此外,还需要符合《欧盟化学品注册、评估、授权和...
如何储存2-氨基-2-(2-吡啶)乙酸乙酯(CAS号:55243-15-7)?
2-氨基-2-(2-吡啶)乙酸乙酯应储存于阴凉、干燥、通风良好的环境中,避免高温和光照。应使用密封容器储存,并远离易燃物、氧化剂和其他危险化学品。
3-羟基-4-甲氧基吡啶-2-羧酸(CAS号:210300-09-7)的主要用途是什么?
3-羟基-4-甲氧基吡啶-2-羧酸主要用于合成其他有机化合物,如药物合成、农药合成和染料合成等。此外,它还可用作中间体和试剂,在化学研究领域也有一定的应用。
来源期刊
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.














