The reaction between W(N) and N: the importance of the adsorption barrier

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2026-10-14 DOI:10.1039/d6cp03221d

Kai-Wen Liu,Bin Yang,Ke-Wei Ding,Xi-Ling Xu,Hong-Guang Xu,Wei-Jun Zheng

引用次数: 0

Abstract

Theoretical calculations indicate that the reaction of W(N2)5− with N2 to form octahedral W(N2)6− is exothermic, which suggests that W(N2)6− is more stable than W(N2)5−. However, our experiments show that the ion signal of W(N2)6− is much weaker than that of W(N2)5−. A detailed theoretical study reveals that there is a weak interaction barrier for adsorption at a W–N distance of about 2.8 Å along the W(N2)5− + N2 reaction pathway, whereas the corresponding neutral reaction, W(N2)5 + N2, is barrierless. The weak interaction barrier is primarily due to repulsion between the electrons in the frontier molecular orbitals of W(N2)5− and N2 at long range. The studies therefore confirm that the formation of octahedral W(N2)6− is hindered by kinetics rather than by thermodynamics.

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W(N)与N的反应：吸附屏障的重要性

理论计算表明，W(N2)5−与N2反应生成八面体W(N2)6−是放热反应，表明W(N2)6−比W(N2)5−更稳定。然而，我们的实验表明，W(N2)6−的离子信号比W(N2)5−弱得多。详细的理论研究表明，W(N2)5−+ N2反应路径在W - n距离约2.8 Å处存在弱相互作用势垒，而W(N2)5 + N2反应则为无势垒。弱相互作用势垒主要是由于W(N2)5−和N2分子边界轨道上的电子在远距离上的排斥作用。因此，这些研究证实了八面体W(N2)6−的形成受到动力学而不是热力学的阻碍。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： 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.