Theoretical investigation of kinetics and branching ratios in i/s/t-C4H9OH reactions with CH3 radical

IF 2.8 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters Pub Date : 2025-06-17 DOI:10.1016/j.cplett.2025.142243

Trong-Nghia Nguyen , Nguyen Thi Minh Hue , Pham Van Tien

引用次数: 0

Abstract

i-, s-, and t-C₄H₉OH are promising biofuels. Their reactions with CH₃ radical were investigated using CCSD(T)//B3LYP/6–311 + G(d,p) calculations and TST/VTST kinetics, including hindered rotation and tunneling corrections. The reactions proceed via hydrogen abstractions with energy barriers of 9.9–15.2 kcal/mol. The kinetic results reveal that abstraction at the CH₃-bearing carbon (β‑carbon) for i-butanol and OH-bearing carbon (α‑carbon) for s-butanol are the dominant channels. In addition, hydrogen abstraction from the oxygen site plays an important role for t-butanol at temperatures below 600 K.

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i/s/t-C4H9OH与CH3自由基反应动力学及支链比的理论研究

i-、s-和t-C4H9OH是很有前途的生物燃料。利用CCSD(T)//B3LYP/ 6-311 + G（d,p）计算和TST/VTST动力学（包括阻碍旋转和隧道修正）研究了它们与CH3自由基的反应。反应通过抽氢进行，能垒为9.9 ~ 15.2 kcal/mol。动力学结果表明，含ch3的碳（β -碳）和含oh的碳（α -碳）是主要的萃取通道。此外，在低于600 K的温度下，从氧位点提取氢对t-丁醇起着重要的作用。

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

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.