以硝铵为中间体在电催化下分解合成叠氮化物。一项cascf和CASPT2研究

IF 2.8 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters Pub Date : 2025-07-08 DOI:10.1016/j.cplett.2025.142281

Juan Soto

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引用次数: 0

摘要

在这项工作中，我们提出硝基离子（带负电荷的亚硝基）是电催化合成叠氮化物分解的中间体。这一论断是基于CASSCF和CASPT2计算得出的，结果表明：(1)（1-氮杂酰基）苯的自由基阴离子比它的中性伙伴能量更稳定[13 kcal/mol]；(2)叠氮基阴离子越过极低势垒[4 kcal/mol]后分解为硝基阴离子和分子氮。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Nitranion as intermediate in the decomposition of azides electrocatalytically synthesized. A CASSCF and CASPT2 study

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Nitranion as intermediate in the decomposition of azides electrocatalytically synthesized. A CASSCF and CASPT2 study

In this work, we propose that nitranion (nitrene negatively charged) is an intermediate in the decomposition of azides electrocatalytically synthesized. This assertion is based on CASSCF and CASPT2 calculations, which show that (1) the radical anion of (1-azidovinyl)benzene is energetically most stable than its neutral partner [13 kcal/mol]; (2) the azidic radical anion decomposes into nitranion and molecular nitrogen after surmounting a very low barrier [4 kcal/mol].

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来源期刊

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

CiteScore

5.70

自引率

3.60%

发文量

798

审稿时长

33 days

期刊介绍： Chemical Physics Letters has an open access mirror journal, Chemical Physics Letters: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. Chemical Physics Letters publishes brief reports on molecules, interfaces, condensed phases, nanomaterials and nanostructures, polymers, biomolecular systems, and energy conversion and storage. Criteria for publication are quality, urgency and impact. Further, experimental results reported in the journal have direct relevance for theory, and theoretical developments or non-routine computations relate directly to experiment. Manuscripts must satisfy these criteria and should not be minor extensions of previous work.