Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO<sub>2</sub> Abstraction Reactions

YIN Geyuan; YOU Jiajun; HU Erjiang; HUANG Zuohua

doi:10.7652/xjtuxb202412020

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Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO₂ Abstraction Reactions

更新时间：2025-07-28

- Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO₂ Abstraction Reactions
- Vol. 58, Issue 12, Pages: 208-216(2024)
- 作者机构：
  
  西安交通大学动力工程多相流国家重点实验室,西安,710049
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb202412020
  CLC： V231.21
- Online First：10 December 2024，
  
  Published：2024
- 稿件说明：
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YIN Geyuan, YOU Jiajun, HU Erjiang, et al. Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO₂ Abstraction Reactions[J]. 2024, 58(12): 208-216. DOI: 10.7652/xjtuxb202412020.
DOI：

YIN Geyuan, YOU Jiajun, HU Erjiang, et al. Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO₂ Abstraction Reactions[J]. 2024, 58(12): 208-216. DOI: 10.7652/xjtuxb202412020. DOI：

摘要

针对偏二甲肼与N

化学反应动力学模型的不准确问题

开展了关键反应的高精度量子化学计算。首先

基于从头算方法

开展了偏二甲肼单分子分解及NO

脱氢反应速率常数计算

利用CCSD(T)/cc-pVTZ//B2PLYPD3/6-311++G(d

p)计算级别得到反应体系的势能面; 接着

采用多参考态方法和CASPT2/CBS//CASPT2/cc-pVTZ计算级别

修正了无势垒反应的势能面; 最后

通过气相单分子反应理论/主方程理论求解温度和压力相关的速率常数

采用变分过渡态理论求解无势垒反应的速率常数。数值结果表明:计算得到的速率常数与实验结果吻合良好

得到的生成焓与活性热化学表及NIST数据库的结果相差不超过4.18 kJ·mol

-1

熵相差不超过2.09 J·K

-1

·mol

-1

; 偏二甲肼分解的主要反应通道为CH

+CH

NNH

及NH

+CH

NCH

脱氢的关键反应通道为CH

(CH

)NNH

+HONO; 对于低势垒和无势垒反应

相较于传统过渡态理论

变分过渡态理论能够更准确地计算出所有速率常数

并同时给出其在不同压力和温度下的不确定度。研究结果可为火箭发动机燃烧室的数值模拟提供理论支撑。

Abstract

To address the issue of inaccuracies in the kinetic model of the chemical reactions between unsymmetrical dimethylhydrazine and N

high-precision quantum chemical calculations of key reactions are conducted. Initially

employing ab initio m

ethods

the rate coefficients for unsymmetrical dimethylhydrazine decomposition and NO

abstraction reactions are computed. The potential energy surface of the reaction system is determined using the CCSD(T)/cc-pVTZ//B2PLYPD3/6-311++G(d

p)calculation level. Subsequently

the potential energy surface of barrierless reactions is corrected utilizing the multi-reference state method and the CASPT2/CBS//CASPT2/cc-pVTZ calculation level. Finally

temperature and pressure-dependent rate coefficients are obtained employing gas-phase unimolecular reaction theory/master equation theory

and rate coefficients for barrierless reactions are calculated using variational transition state theory. The numerical results demonstrate that the calculated rate coefficients are well aligned with experimental results

with differences in enthalpy of formation not exceeding 4.18 kJ·mol

-1

when compared to data from active thermochemical tables and the NIST database

and entropy differences within 2.09 J·K

-1

·mol

-1

. The primary routes for unsymmetrical dimethylhydrazine decomposition involve the generation of CH

+CH

NNH

and NH

+CH

NCH

. In the NO

dehydrogenation reaction

the pathway leading to CH

(CH

)NNH

+HONO exhibits the highest proportion. Variational transition state theory proves to be more precise in calculating rate coefficients for reactions with low or no barriers than traditional transition state theory

also providing uncertainties across various pressures and temperatures. These research outcomes can provide essential theoretical backing for numerical simulations of rocket engine combustion chambers.

关键词

Keywords

references

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Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO2 Abstraction Reactions

DOI：10.7652/xjtuxb202412020

摘要

Abstract

关键词

Keywords

references

Calculation of Rate Coefficients for Unsymmetrical Dimethylhydrazine Decomposition and NO₂ Abstraction Reactions