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3237503 
Journal Article 
Radical-radical reactions NCO (X-2 Pi) + Cl (P-2(u)): Mechanistic study 
Wang, DeQ; Li, Yan; Huang, XuRi; Liu, HuiL; Sun, CC 
2009 
1 
Journal of Molecular Structure: Theochem
ISSN: 0166-1280
EISSN: 1872-7999 
897 
1-3 
111-117 
WOS:000264385800021 
The reaction of isocyanato radical, NCO (X-2 Pi) with
chlorine atom, Cl (P-2(u)) is investigated by ab initio, quantum chemistry methods. The important
triplet potential energy surfaces (PES) are calculated at the CCSD(T)/aug-cc-pVQZ//CCSD/6-311++G
(**)+ZPE levels. On the triplet PES of the title reaction, the most possible pathway is via
(TSR)-T-3-1 forming the cis isomer (3)1, and then (3)1 can lead to the lower trans isomer 32 via
transition state (3)TS1-2, followed by the transition state (3)TS2-P1 to get the important
product P1 with larger exothermic. The other reaction pathways are less competitive due to
thermodynamical or kinetic factors. The possible singlet-triplet intersystem crossing is also
discussed. We expect this contribution can lead us to deeply understand the mechanism of the
title reaction and may be helpful for the modeling of isocyanato radical-halogen combustion
chemistry. (c) 2008 Elsevier B.V. All rights reserved. 
Reaction mechanism; Potential energy surface; Cl radical; NCO radical