A quantitative curve-crossing model for radical fragmentation

Edward D. Lorance, Ian Gould

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The kinetics of bond fragmentation for a series of N-methoxypyridyl radicals are analyzed in terms of a simple curve-crossing model that includes bond stretching and bond bending coordinates. The model accurately reproduces the reaction surfaces calculated using density functional theory (DFT) and also the experimental reaction energy barriers. The reactions proceed on the ground state surface by avoidance of a conical intersection, which is clearly illustrated by the model. A value for the electronic coupling matrix element responsible for splitting the upper and lower surfaces of 0.9 eV is obtained. The model illustrates the molecular features that allow barrierless fragmentation from a formally π* radical.

Original languageEnglish (US)
Pages (from-to)2912-2919
Number of pages8
JournalJournal of Physical Chemistry A
Volume109
Issue number12
DOIs
StatePublished - Mar 31 2005

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fragmentation
curves
avoidance
Energy barriers
Surface reactions
intersections
Ground state
surface reactions
Stretching
Density functional theory
density functional theory
Kinetics
ground state
kinetics
matrices
electronics
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

A quantitative curve-crossing model for radical fragmentation. / Lorance, Edward D.; Gould, Ian.

In: Journal of Physical Chemistry A, Vol. 109, No. 12, 31.03.2005, p. 2912-2919.

Research output: Contribution to journalArticle

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