V. Kovalskii, A. A. Shubin, Y. Chen, D. Ovchinnikov, S. Ph. Ruzankin, J. Hasegawa, I. Zilberberg, V. N. Parmon
Reactivity of the [FeO]2+ group in the abstraction of hydrogen from methane is determined by metastable oxyl state FeIII-O* causing the negative spin polarization of the methyl moiety as was shown by quantum-chemical means with the use of model iron hydroxide species FeO(OH)2, Fe2O(OH)5, and Fe4O5(OH)3 as an example.
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This account presents author's opinion on the mechanism of the H-abstraction from methane by the [FeO](2+) group. In the course of reaction with hydrogen, the Fe-O bond in the ferryl configuration becomes elongated causing transfer of the spin-up electron from one of doubly occupied bonding orbitals leaving behind single spin-down electron on oxygen. This oxygen in so-formed oxyl configuration of the [FeO](2+) moiety then easily accept the spin-up hydrogen atom from methane in the same way as the radical-localized oxygen does. This mechanism is compared with the scheme in which the hydrogen is…
Silanol nests can play the role of places into which positively charged groups, such as, [FeO]2+, can invade. In the framework of this work, the influence of such structures on the activity of the [FeO]2+ group in the reaction of detachment of a hydrogen atom from methane was considered. Two ways of the reaction of hydrogen atom transfer (HAT) from methane were found: the so-called ferryl and oxyl routes. It was shown that the reaction of the detachment of a hydrogen atom from methane, which is a limiting stage of the oxidation of methane to methanol at the alpha center, proceeds through the f…
We report differences in adsorption and reaction energetics for ethylene on Si(001) with respect to different dangling bond configurations induced by hydrogen precoverage as obtained via density functional theory calculations. This can help to understand the influence of surface defects and precoverage on the reactivity of organic molecules on semiconductor surfaces in general. Our results show that the reactivity on surface dimers fully enclosed by hydrogen covered atoms is essentially unchanged compared to the clean surface. This is confirmed by our scanning tunnelling microscopy measurement…
Hydrogen-atom roaming reactions in water clusters: Unveiling an unusual dimension of water reactivity through first-principles calculations and machine learning
研究通过从头计算和机器学习揭示水簇中氢原子游离反应，发现游离机制在水中的存在，补充了水反应机制的基本维度。
The O-O coupling process is considered on terminal monocoordinated oxo centers in the gamma FeOOH hydroxide modeled by iron tetramer cubane cluster with the Fe4O4 core. The density functional theory predicts that reactive HO-Fe(IV)-O$\bullet$ group formed from hydroxide by second withdrawal of proton-electron pair is capable to couple the OH moiety of water molecule with a low barrier. This process is far more effective than direct coupling of oxo centers on neighboring metal sites and is comparable with the coupling between terminal oxo center and three-coordinated lattice oxo center. The com…
The detection, removal and reduction of hydrogen peroxide is of significant importance for its increasing application in the areas of environment, food, electrochemistry and clinical laboratory. Herein the dissociative adsorption behavior of hydrogen peroxide on ultrathin magnesia (001) films deposited on transition metal is uncovered for the first time by employing periodic density-functional theory calculations with van der Waals corrections. The hydrogen peroxide is dissociated smoothly and reduced to surface hydroxyls on MgO(001)/TM, and the dissociative adsorption energies of all the cons…
Beyond potential energy surface benchmarking: a complete application of machine learning to chemical reactivity
针对传统机器学习势能面依赖化学直觉数据而不完整的问题，提出基于元动力学的主动学习负向设计策略，构建混合模型实现氢燃烧反应预测，成本降两个数量级。
Mode-Specific Dynamics of $\text{CO}_2$ Hydrogenation on Copper: The Hidden Role of Molecular Rotation
该研究基于全维第一性原理神经网络势能面，揭示铜表面CO2加氢反应中分子旋转激发的主导作用，修正了传统机理解释，为CO2加氢的精准控制提供了基础。
Atmospheric Pressure Ammonia Synthesis on AuRu Catalysts Enabled by Plasmon-Controlled Hydrogenation and Nitrogen-species Desorption
本研究提出可见光驱动的AuRu双金属等离激元合金，在常温常压下通过热电子促进氮物种加氢和氢辅助N₂裂解实现氨合成。
Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling
本研究首次在振动强耦合条件下实验考察了CN自由基与氯仿的基元双分子反应，发现强耦合未显著改变反应速率，为理解腔调制化学反应机制提供了重要见解。
Understanding the complex chemistry of functional nanomaterials is of fundamental importance. Controlled synthesis and characterization at the atomic level is essential to gain deeper insight into the unique chemical reactivity exhibited by many nanomaterials. Cerium oxide nanoparticles have many industrial and commercial applications,resulting from very strong catalytic, pro-and anti-oxidant activity. However, the identity of the active species and the chemical mechanisms imparted by nanoceria remain elusive, impeding the further development of new applications. Here, we explore the behavior …
Resonant inelastic x-ray scattering (RIXS) provides remarkable opportunities to interrogate ultrafast dynamics in liquids. Here we use RIXS to study the fundamentally and practically important hydroxyl radical in liquid water, OH(aq). Impulsive ionization of pure liquid water produced a short-lived population of OH(aq), which was probed using femtosecond x-rays from an x-ray free-electron laser. We find that RIXS reveals localized electronic transitions that are masked in the ultraviolet absorption spectrum by strong charge-transfer transitions -- thus providing a means to investigate the evol…
Many astrochemical models today explicitly consider the species that comprise the bulk of interstellar dust grain ice-mantles separately from those in the top few monolayers. Bombardment of these ices by ionizing radiation - whether in the form of cosmic rays, stellar winds, or radionuclide emission - represents an astrochemically viable means of driving a rich chemistry even in the bulk of the ice-mantle, now supported by a large body of work in laboratory astrophysics. In this study, using an existing rate equation-based astrochemical code modified to include a method of considering radiatio…
Here we describe a computational study undertaken in an effort to elucidate the reaction mechanisms behind the experimentally observed oxidations and hydrations catalyzed by graphene oxide (GO). Using the oxidation of benzyl alcohol to benzaldehyde as a model reaction, density functional theory (DFT) calculations revealed that this reactivity stemmed from the transfer of hydrogen atoms from the organic molecule to the GO surface. In particular, neighbouring epoxide groups decorating GO's basal plane were ring-opened, resulting in the formation of diols, followed by dehydration. Consistent with…
Boron-doped graphene -- DFT study of the role of dopant concentration and oxidation on sodium and aluminium storage applications
本文利用DFT计算研究硼掺杂浓度和氧化对石墨烯反应活性、电导率及钠/铝存储性能的影响，发现硼掺杂和氧化可将钠存储容量提高至4倍。
Accurate prediction of the electronic and hydrogen storage properties of linear carbon chains (Cn) and Li-terminated linear carbon chains (Li2Cn), with n carbon atoms (n = 5 - 10), has been very challenging for traditional electronic structure methods, due to the presence of strong static correlation effects. To meet the challenge, we study these properties using our newly developed thermally-assisted-occupation density functional theory (TAO-DFT), a very efficient electronic structure method for the study of large systems with strong static correlation effects. Owing to the alteration of the …
The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of Chemistry, Biology and Atmospheric Science. Nevertheless, the electronic structure of such species is a challenge for ab-initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties,…
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