Orbital Energy-Based Reaction Analysis of SN2 Reactions
Fuel Cell Nanomaterials Center, University of Yamanashi, Kofu 400-0021, Japan
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
Author to whom correspondence should be addressed.
Academic Editors: Karlheinz Schwarz and Agnes Nagy
Received: 1 June 2016 / Revised: 28 June 2016 / Accepted: 29 June 2016 / Published: 8 July 2016
An orbital energy-based reaction analysis theory is presented as an extension of the orbital-based conceptual density functional theory. In the orbital energy-based theory, the orbitals contributing to reactions are interpreted to be valence orbitals giving the largest orbital energy variation from reactants to products. Reactions are taken to be electron transfer-driven when they provide small variations for the gaps between the contributing occupied and unoccupied orbital energies on the intrinsic reaction coordinates in the initial processes. The orbital energy-based theory is then applied to the calculations of several
2 reactions. Using a reaction path search method, the Cl−
I → ClCH3
reaction, for which another reaction path called “roundabout path” is proposed, is found to have a precursor process similar to the roundabout path just before this SN
2 reaction process. The orbital energy-based theory indicates that this precursor process is obviously driven by structural change, while the successor SN
2 reaction proceeds through electron transfer between the contributing orbitals. Comparing the calculated results of the SN
2 reactions in gas phase and in aqueous solution shows that the contributing orbitals significantly depend on solvent effects and these orbitals can be correctly determined by this theory.
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MDPI and ACS Style
Tsuneda, T.; Maeda, S.; Harabuchi, Y.; Singh, R.K. Orbital Energy-Based Reaction Analysis of SN2 Reactions. Computation 2016, 4, 23.
Tsuneda T, Maeda S, Harabuchi Y, Singh RK. Orbital Energy-Based Reaction Analysis of SN2 Reactions. Computation. 2016; 4(3):23.
Tsuneda, Takao; Maeda, Satoshi; Harabuchi, Yu; Singh, Raman K. 2016. "Orbital Energy-Based Reaction Analysis of SN2 Reactions." Computation 4, no. 3: 23.
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