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IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-04-01 DOI:10.1016/j.molliq.2025.127491

Kai Diao , Wenlei Cao , Xia Qiu , Mei Yang , Shunping Shi , Deliang Chen

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引用次数: 0

摘要

在 PBE0-D3/Def2TZVP 水平上进行的 DFT 计算表明，TM4（TM = Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd）团簇的全局最小结构是四面体和平面结构。基于 Hirshfeld 分区的独立梯度模型（IGMH）结果表明，在 TM4@H2O 水合物中，水分子与簇表面发生化学键合，但在 Cd4@H2O 水合物中则通过范德华力发生吸附。在 TM4 + H2O 反应中，Zr4 + H2O 反应是一种自发放热解离反应，其性能最好，反应能量为 -5.646 eV。在反应过程中考虑了自旋多重跃迁，发现 Mo4 + H2O、Pd4 + H2O 和 Nb4 + H2O 反应具有两态反应性。Pd4 + H2O 反应有效地降低了反应能垒，而 Mo4 + H2O 和 Nb4 + H2O 反应则显示出多种反应途径的可能性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Mechanism of water molecule dissociation on transition metal cluster surfaces based on density functional theory

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Mechanism of water molecule dissociation on transition metal cluster surfaces based on density functional theory

DFT calculations at the PBE0-D3/Def2TZVP level show that the global minimum structures of TM₄ (TM = Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd) clusters are tetrahedral and planar. Independent gradient model based on Hirshfeld partition (IGMH) results indicate that, in TM₄@H₂O hydrates, water molecules are chemically bonded to the cluster surface, except in Cd₄@H₂O hydrates where adsorption occurs via van der Waals forces. In TM₄ + H₂O reactions, the Zr₄ + H₂O reaction is a spontaneous exothermic dissociation with the best performance, having a reaction energy of −5.646 eV. The spin multiplicity transitions were considered during the reaction process, revealing two-state reactivity in the Mo₄ + H₂O, Pd₄ + H₂O, and Nb₄ + H₂O reactions. The Pd₄ + H₂O reaction effectively lowers the reaction energy barrier, while the Mo₄ + H₂O and Nb₄ + H₂O reactions exhibit the possibility of multiple reaction pathways.

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.