Mechanism and Energetics of 1,2-Addition
of Dioxygen ¹O₂(¹g) to Ethylene

S. P. Dolin, N. N. Breslavskaya, A. A. Markov,
T. Yu. Mikhailova, N. I. Moiseeva, and A. E. Gekhman

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 117907 Russia

e-mail: dolin@igic.ras.ru

Received May 20, 2015

Abstract—The optimal geometry and energy parameters for five electronic states of the {¹O₂(¹g) + C₂H₄}
system that characterize the elementary reactions of two-step 1,2-addition giving the dioxetane molecule were
calculated using various quantum chemical methods (RHF, B3LYP, MPn, n = 2–4, QCISD, and CCSD) and
basis sets (from 6-31+G(d,p) to 6-311+G(3df,2p) and pVTZ). The first step of the reaction was found to pass
through the ethylene perepoxide intermediate. Considering experimental and published calculated data, the
dependence of the results on the calculation procedure was exampled. The higher-level methods (QCISD,
CCSD, CASSCF) and the standard methods (DFT, MPn) were found to reliably lead to virtually the same
description of the energetics of this two-step reaction corresponding to experimental estimates.

DOI: 10.1134/S0036023615120104

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