A combined crossed beam and theoretical investigation of O(3P) + (CH3)2CH -> C3H6 + OH
- 주제(키워드) crossed beam study
- 발행기관 고려대학교 대학원
- 지도교수 최종호
- 발행년도 2011
- 학위수여년월 2011. 2
- 학위구분 석사
- 학과 일반대학원 화학과
- 세부전공 물리화학 전공
- 원문페이지 40 p
- 실제URI http://www.dcollection.net/handler/korea/000000024844
- 본문언어 영어
- 제출원본 000045640141
초록/요약
The radical-radical reaction dynamics of ground-state atomic oxygen [O(3P)] with iso-propyl radicals, (CH3)2CH has been investigated in a crossed beam configuration and ab initio theoretical calculation. The radical reactants O(3P) and (CH3)2CH were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of precursor iso-propyl bromide, respectively. The nascent distributions of OH (X2Π: υ = 0) from the major reaction channel O(3P) + (CH3)2CH → C3H6 (propene) + OH showed substantial internal excitations with a bimodal feature of low- and high-N˝ components with neither spin-orbit nor Λ-doublet propensities. Unlike previous kinetic results, proposed to proceed only through the direct H-atom abstraction process, on the basis of the population analysis and comparison with the statistical theory, the title reaction can be described in terms of two competing mechanisms at the molecular level. The major low N˝-components can be described in terms of the direct abstraction process responsible for the comparable vibrational populations, while the minor but hot rotational distribution of the high N˝-components implies that some fraction of radical reactants is sampled to proceed through the short-lived addition-complex forming process.
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CONTENTS
Abstract
1. Introduction
2. Experiment
3. Ab initio Calculations
4. Experimental results and analysis
A. Nascent Rotational Distributions
B. Spin-orbit and Λ-doublet propensities
5. Discussion
A. Reaction Pathways On the Ab initio Potential Energy Suface
B. Prior and Surprisal analyses: Statistical versus Dynamic
C. Reaction Mechanism
6. Summary
7. References
