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American Chemical Society, The Journal of Physical Chemistry A, 27(118), p. 5122-5123, 2014

DOI: 10.1021/jp503958z

American Chemical Society, The Journal of Physical Chemistry A, 51(119), p. 12906-12907, 2015

DOI: 10.1021/acs.jpca.5b10449

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Comment on "Computational Study on the Vinyl Azide Decomposition"

Journal article published in 2014 by Curt Wentrup, Claudio M. Nunes ORCID, Igor Reva, Minh Tho Nguyen, Tran Dieu Hang, Nina P. Gritsan ORCID, Vitaly G. Kiselev ORCID
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This paper is available in a repository.

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Abstract

We would like to comment on the recent paper 'Computational Study on the Vinyl Azide Decomposition'' (J. Phys. Chem. A 2014, 118, 5038-5045) and a subsequent Comment (J. Phys. Chem. A 2014, 118, 5122-5123). We wish to point out that single-reference quantum chemical methods were found to be suitable for study of primary thermolysis reactions of VA. However, the DFT (B3LYP functional) and especially MP2 methods tend to substantially overestimate the energy barriers for N2 elimination. Moreover, the authors of both previous papers missed an energetically low-lying entrance channel of VA, which should carefully be scrutinized in forthcoming studies. In addition, speculations on the role of MECP and of the singlet and triplet vinyl nitrene in decomposition mechanism of VA are irrelevant.