Jump to main content
Jump to site search

Issue 2, 2020
Previous Article Next Article

Calculations on the unimolecular decomposition of the nerve agent VX

Author affiliations

Abstract

It is very difficult to perform experiments on the physical parameters for the thermal decomposition of chemical nerve agents such as VX and computations, therefore, are useful. The reaction dynamics of the gas-phase pericyclic hydrogen transfer of the nerve agent VX is studied computationally. The geometries of the stationary structures are calculated at M06-2X/jul-cc-pVTZ level of theory. Single point energy calculations are carried out at the CBS/QB3 level to correct the energy barriers. Canonical reaction rate constants are calculated as a function of temperature. The one-dimensional semiclassical transition state theory is used to analyse the quantum tunneling effects. A reduced-dimensional hindered rotor model is proposed, tested, and applied to calculate the vibrational partition functions. It is found that the ester (O-side) and thioester (S-side) side chains of VX undergo pericyclic H-transfer reactions that result in decomposition of the molecule. The S-side reaction is favoured both kinetically and thermodynamically and dominates the pyrolysis over the temperature range from 600 K to 1000 K. It is predicted that VX completely decomposes in 2 s at temperatures above 750 K.

Graphical abstract: Calculations on the unimolecular decomposition of the nerve agent VX

Back to tab navigation

Supplementary files

Article information


Submitted
16 Sep 2019
Accepted
17 Nov 2019
First published
17 Dec 2019

This article is Open Access

Phys. Chem. Chem. Phys., 2020,22, 564-574
Article type
Paper

Calculations on the unimolecular decomposition of the nerve agent VX

X. Shan, M. R. Sambrook and D. C. Clary, Phys. Chem. Chem. Phys., 2020, 22, 564
DOI: 10.1039/C9CP05109K

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements