Exploring the multiple reaction pathways for the H + cyc-C 3H 6 reaction

Hua Gen Yu, James Muckerman

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Reaction pathways for the hydrogen atom plus cyclopropane (cyc-C 3H 6) reaction are studied using an extrapolated coupled-cluster/complete basis set (CBS) method based on the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets. For this activated reaction, results reveal two reaction mechanisms, a direct H-abstraction and a H-addition/ring-opening. The hydrogen-abstraction reaction yields the H 2 and cyclopropyl (cyc-C 3H 5) radical products. The vibrationally adiabatic ground-state (VAG) barrier height is predicted to be 13.03 kcal/mol. The isomerization barrier height from the product cyclopropyl to allyl radical is 21.98 kcal/mol via a cyc-C 3H 5 ring-opening process. In addition, the H-addition and ring-opening mechanism will lead to an n-C 3H 7 radical, which can result in a variety of products such as CH 3 + C 2H 4, H + CH 3CHCH 2, and H 2 + C 3H 5, etc. The VAG barrier height of the H-addition reaction is 16.49 kcal/mol, which is slightly higher than that of the direct H-abstraction reaction. Although the H + cyc-C 3CH 6 → CH 4CH reaction is exoergic by 11.90 kcal/mol, this reaction is unlikely due to a high barrier of 43.05 kcal/mol along the minimum energy path.

Original languageEnglish
Pages (from-to)10844-10849
Number of pages6
JournalJournal of Physical Chemistry A
Volume108
Issue number49
DOIs
Publication statusPublished - Dec 9 2004

Fingerprint

Ground state
Hydrogen
Addition reactions
Isomerization
Atoms
methylidyne
rings
products
cyclopropane
ground state
isomerization
hydrogen atoms
hydrogen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Exploring the multiple reaction pathways for the H + cyc-C 3H 6 reaction. / Yu, Hua Gen; Muckerman, James.

In: Journal of Physical Chemistry A, Vol. 108, No. 49, 09.12.2004, p. 10844-10849.

Research output: Contribution to journalArticle

@article{d58184eb3c9549b9bfaeae8c3c0e13f5,
title = "Exploring the multiple reaction pathways for the H + cyc-C 3H 6 reaction",
abstract = "Reaction pathways for the hydrogen atom plus cyclopropane (cyc-C 3H 6) reaction are studied using an extrapolated coupled-cluster/complete basis set (CBS) method based on the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets. For this activated reaction, results reveal two reaction mechanisms, a direct H-abstraction and a H-addition/ring-opening. The hydrogen-abstraction reaction yields the H 2 and cyclopropyl (cyc-C 3H 5) radical products. The vibrationally adiabatic ground-state (VAG) barrier height is predicted to be 13.03 kcal/mol. The isomerization barrier height from the product cyclopropyl to allyl radical is 21.98 kcal/mol via a cyc-C 3H 5 ring-opening process. In addition, the H-addition and ring-opening mechanism will lead to an n-C 3H 7 radical, which can result in a variety of products such as CH 3 + C 2H 4, H + CH 3CHCH 2, and H 2 + C 3H 5, etc. The VAG barrier height of the H-addition reaction is 16.49 kcal/mol, which is slightly higher than that of the direct H-abstraction reaction. Although the H + cyc-C 3CH 6 → CH 4CH reaction is exoergic by 11.90 kcal/mol, this reaction is unlikely due to a high barrier of 43.05 kcal/mol along the minimum energy path.",
author = "Yu, {Hua Gen} and James Muckerman",
year = "2004",
month = "12",
day = "9",
doi = "10.1021/jp0458194",
language = "English",
volume = "108",
pages = "10844--10849",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "49",

}

TY - JOUR

T1 - Exploring the multiple reaction pathways for the H + cyc-C 3H 6 reaction

AU - Yu, Hua Gen

AU - Muckerman, James

PY - 2004/12/9

Y1 - 2004/12/9

N2 - Reaction pathways for the hydrogen atom plus cyclopropane (cyc-C 3H 6) reaction are studied using an extrapolated coupled-cluster/complete basis set (CBS) method based on the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets. For this activated reaction, results reveal two reaction mechanisms, a direct H-abstraction and a H-addition/ring-opening. The hydrogen-abstraction reaction yields the H 2 and cyclopropyl (cyc-C 3H 5) radical products. The vibrationally adiabatic ground-state (VAG) barrier height is predicted to be 13.03 kcal/mol. The isomerization barrier height from the product cyclopropyl to allyl radical is 21.98 kcal/mol via a cyc-C 3H 5 ring-opening process. In addition, the H-addition and ring-opening mechanism will lead to an n-C 3H 7 radical, which can result in a variety of products such as CH 3 + C 2H 4, H + CH 3CHCH 2, and H 2 + C 3H 5, etc. The VAG barrier height of the H-addition reaction is 16.49 kcal/mol, which is slightly higher than that of the direct H-abstraction reaction. Although the H + cyc-C 3CH 6 → CH 4CH reaction is exoergic by 11.90 kcal/mol, this reaction is unlikely due to a high barrier of 43.05 kcal/mol along the minimum energy path.

AB - Reaction pathways for the hydrogen atom plus cyclopropane (cyc-C 3H 6) reaction are studied using an extrapolated coupled-cluster/complete basis set (CBS) method based on the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets. For this activated reaction, results reveal two reaction mechanisms, a direct H-abstraction and a H-addition/ring-opening. The hydrogen-abstraction reaction yields the H 2 and cyclopropyl (cyc-C 3H 5) radical products. The vibrationally adiabatic ground-state (VAG) barrier height is predicted to be 13.03 kcal/mol. The isomerization barrier height from the product cyclopropyl to allyl radical is 21.98 kcal/mol via a cyc-C 3H 5 ring-opening process. In addition, the H-addition and ring-opening mechanism will lead to an n-C 3H 7 radical, which can result in a variety of products such as CH 3 + C 2H 4, H + CH 3CHCH 2, and H 2 + C 3H 5, etc. The VAG barrier height of the H-addition reaction is 16.49 kcal/mol, which is slightly higher than that of the direct H-abstraction reaction. Although the H + cyc-C 3CH 6 → CH 4CH reaction is exoergic by 11.90 kcal/mol, this reaction is unlikely due to a high barrier of 43.05 kcal/mol along the minimum energy path.

UR - http://www.scopus.com/inward/record.url?scp=10844228181&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=10844228181&partnerID=8YFLogxK

U2 - 10.1021/jp0458194

DO - 10.1021/jp0458194

M3 - Article

VL - 108

SP - 10844

EP - 10849

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 49

ER -