STRUCTURE OF THE HOO–N=N–OOH INTERMEDIATE IN HYDROGEN PEROXIDE ACTIVATION OF N2: QUANTUM CHEMICAL DFT CALCULATIONS
I. I. Zakharov, M. G. Loriya, A. B. Tselishchev
Keywords: density functional theory (DFT) method, НОО and О2 high energy states, activation of N2, molecular and spectroscopic parameters, HOO–N=N–OOH intermediate, hydroxyl radical spillover
Abstract
Quantum chemical calculations of the electronic and geometric structure of the HOO–N=N–OOH intermediate in the activation reaction of molecular nitrogen are performed by the density functional theory method at the B3LYP/6-311++G(3df,3pd) level. For HOO–*N=N*–OOH isotopomers with respect to nitrogen the spectroscopic parameters of the intermediate are characterized, which indicate the possibility of its experimental detection. The reactivity of the high energy state НОО* (2A') in the activation of N2 is analyzed. The possibility of the generation of singlet oxygen О2(1Δg ) is considered in the dimerization of radicals with the ground state НОО (2A") followed by the sensitization of excited НОО* (2A'). A substantiated process of bonding of molecular nitrogen is given as an example of the self-organization of a chemical system in the activation of a hard-to-oxidize N2 substance.
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