Decomposition Mechanisms of Hyponitrite Molecules: Multireference investigations

Hao-Yu Kuo1, Jen-Shiang K. Yu*,1,2 and Gou-Tao Huang*,1,2

1Institute of Bioinformatics and Systems Biology, and 2Center For Intelligent Drug Systems and Smart Bio-devices (IDS2B), National Yang Ming Chiao Tung University

Hyponitrite(N2O22) and hyponitrite radical(N2O2•) are metastable compounds in biological and environmental redox processes that involve nitric oxide(NO˙). Decomposition of N2O2• has been proposed to involve direct C–O bond cleavage or by an auto-redox reaction.1, 2 Multireference approaches are employed to study the two pathways. The computed energies for vertical electron attachment and detachment of N2O2•are 4.7 and 3.1 eV, respectively, which excludes the possibility of the auto-redox reaction. In addition, scan calculations are performed to characterize homolytic or heterolytic bond dissociation. The results help us understand chemistry of hyponitrite molecules, particularly related to formation of nitric oxide.