Theoretical Study on the Mechanism of NH + HCNO Reaction

Abstract:

DFT B3LYP calculations with the 6-311G(d, p) basis set were carried out to explore the mechanism of the NH (X3Σ-) + HCNO reaction. On the basis of calculated reaction paths, the three reaction channels are predicted to occur via the following reaction steps. The NH radical initially attacks C atom of the HCNO radical, leading to an intermediate HC(NH)NO (a1), followed by formation of a bond between the H atom of NH (X3Σ-) radical and the N atom of HCNO, leading to the formation of product HNO + HCN. In addition to the H atom of NH (X3Σ-) radical migration in the intermediate HC(NH)NO (a1), the H atom migration from C atom to N atom leads to an intermediate HN(H)CNO (b), followed by rupture of H2N－CNO bond, leading to the products NH2 + CNO. The NH radical initially attacks N atom of the HCNO radical, leading to an intermediate HCN(NH)O (a3), followed by formation of the products CH2O + N2, through the intermediates d1, d2, d3, d4, e1, e2 and f. The CCSD(T)/ 6-311G(d,p) energetic results indicated that the total barrier of product 1, product 2 and product 3 is 32.8 kcal/mol, 89.5 kcal/mol, 40.0 kcal/mol, respectively. It is shown that P1(CH2O + N2), P3 (HCN + HNO) are the major product channels with a minor contribution from P2 (NH2 + CNO).

• Periodical: Advanced Materials Research (Volumes 396-398)
• Pages: 997-1000
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.396-398.997
• Online since: November 2011
• Authors: Xiao Di Niu, Can Can Sun, Jing Long Tang, Hong Su Wang
• Keywords: Mechanism, NH + HCNO, Potential Energy Surface (PES)

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