Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

5-2000

Journal or Book Title

Journal of Physical Chemistry A

Volume

104

Issue

23

First Page

5647

Last Page

5650

DOI

10.1021/jp0004361

Abstract

The potential energy surfaces and the nature of transition structures for the decomposition of three N8 isomers (octaazapentalene, azidopentazole, and diazidodiimide) into 4 N2 are investigated using ab initio methods. These isomers are all high-energy species, relative to molecular nitrogen, but are much lower in energy than the previously studied cubic structure. Second-order perturbation theory (MP2) predicts that the dissociation of octaazapentalene proceeds via isomerization to a linear molecule. The dissociation reaction of azidopentazole prefers ring breaking, at a cost of less than 20 kcal/mol, to breaking a bond in the side chain. The cis isomer of diazidodiimide is found to be slightly more stable than that of the trans isomer at the highest levels of theory used here. The coupled cluster (CCSD(T)) diazidodiimide dissociation barrier is computed to be about 20 kcal/mol. This barrier is only marginally sufficient to make this high energy density molecule metastable.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 104 (2000): 5647, doi:10.1021/jp0004361. Copyright 2000 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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