文献类型：期刊文献

英文题名：Study on the Intramolecular H-Migration Kinetics of Strained Polycyclic Hydrocarbons with Distinct Cis and Trans Configurations

作者：Yao, Xiaoxia Xuan, Ying Guo, Junjiang Liu, Mingxia Li, Zerong Li, Zhian

第一作者：Yao, Xiaoxia

通信作者：Li, Z[1];Li, ZR[2]

机构：[1]Chengdu Aeronaut Polytech Univ, Aviat Maintenance Ind Coll, Chengdu 610100, Peoples R China;[2]Guizhou Inst Technol, Sch Chem Engn, Guiyang 550003, Peoples R China;[3]Chongqing Univ Technol, Sch Phys & New Energy, Chongqing 401135, Peoples R China;[4]Sichuan Univ, Coll Chem, Chengdu 610064, Peoples R China

第一机构：Chengdu Aeronaut Polytech Univ, Aviat Maintenance Ind Coll, Chengdu 610100, Peoples R China

通信机构：corresponding author), Chengdu Aeronaut Polytech Univ, Aviat Maintenance Ind Coll, Chengdu 610100, Peoples R China;corresponding author), Sichuan Univ, Coll Chem, Chengdu 610064, Peoples R China.

年份：2026

卷号：31

期号：13

外文期刊名：MOLECULES

收录：;Scopus(收录号：2-s2.0-105044550782);WOS:【SCI-EXPANDED(收录号:WOS:001817833000001)】；

基金：This research is funded by the 2025 Second Batch Scientific Research Startup Fund Project for High-Level Talents of Chengdu Aeronautic Polytechnic University: High-Temperature Reaction Kinetics of Soot Precursors in Aeroengine Combustors (Grant No. ZZX0625170), Personal Scientific Research Start-up Fund-the 2025 High-Level Talent Team Construction Fund Project of Chengdu Aeronautic Polytechnic University (Grant No. G1060312), the National Natural Science Foundation of China (Grant No. 22569004), and the Natural Science Foundation of Chongqing (Grant No. CSTB2025NSCQ-GPX0973).

语种：英文

外文关键词：strained polycyclic hydrocarbo; intramolecular H-migration reaction; cis and trans configuration; reaction barrier; high-pressure-limit rate constant

摘要：High-energy-density fuels (HEDFs) have garnered considerable interest in aerospace fields, primarily due to their superior density and volumetric net heat of combustion (NHOC) compared with traditional petroleum-based fuels. Strained polycyclic hydrocarbons are regarded as one of the most crucial categories of HEDF. As an isomer (C10H16) of JP-10, the target compound is composed of two cyclopropyl rings and one cyclobutyl ring connected in a linear manner. Notably, intramolecular H-migration reactions of peroxyl radicals derived from strained polycyclic hydrocarbons (C10H15OO center dot) are of great significance for establishing the reaction mechanism of high-energy-density fuels over a broad temperature range. In this work, the intramolecular H-migration kinetics of C10H15OO center dot with distinct cis and trans configurations are investigated by quantum chemical calculations. Geometry optimization and frequency calculations are carried out for all species using the M06-2X/6-311++G(d,p) level of theory, while single-point energy calculations are performed at the CBS-QB3 level. Our calculated results demonstrate that different types of intramolecular H-migration reactions exhibit significant differences in barrier heights. Based on the ring structures where the reaction centers are located, these reactions can be classified into three categories: the lowest barriers correspond to H-migration reactions occurring between the central cyclopropyl ring and the terminal cyclobutyl ring; the highest barriers correspond to H-migration reactions confined entirely within the terminal cyclobutyl ring; and the barriers for H-migration reactions occurring between the terminal cyclopropyl ring and the central cyclopropyl ring lie between the above two. High-pressure-limit rate constants for 33 elementary reactions are determined in the temperature range of 500 to 2500 K based on the conventional transition-state theory (TST) and expressed in the modified Arrhenius form.