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Theoretical Study on the Mechanism of the 1CHF + NO Reaction

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journal contribution
posted on 10.10.2001, 00:00 by Jian-jun Liu, Yi-hong Ding, Ji-kang Feng, Chia-chung Sun
The complex doublet potential energy surface of the CHFNO system is investigated at the QCISD(T)/6-311G(df,p)//B3LYP/6-311G(d,p) level in order to explore the possible reaction mechanism of 1CHF radical with NO. Twenty-six minimum isomers and fifty-nine transition states are located. Various possible reaction pathways are probed. It is shown that five dissociation products P1 HF + NCO, P2 F + HNCO, P4 OH + FCN, P5 F + HOCN, and P7 3NH + FCO are both thermodynamically and kinetically accessible. Among the five dissociation products, P2 and P4 may be the most abundant products with comparable quantities, whereas P1 is much less competitive followed by the almost negligible P5 and P7. Our results are in marked difference from previous experimental observation that only two dissociation products P1 and P2 are identified with the branching ratio being 6:4. However, and despite some energetic differences, our calculated potential energy surface features are quite in parallel to those of the analogous reaction 3CH2 + NO that has been extensively studied. Therefore, future experimental reinvestigations are desirable to clarify the mechanism of the title reaction. The present study may be useful for understanding the CHF chemistry.