Conformational analysis for hydrated ethylene oxide oligomer models by quantum chemical calculations

Abstract

Hydrate effects on the conformations of ethylene oxide oligomers (EO-x, x = 1–8 mers) were examined using quantum chemical calculations (QCC). Conformational analyses were carried out by RHF/6-31G. The models were constructed by locating a water molecule to each ether–oxygen in the structures optimized for non-hydrate oligomers. Hydrate ratio, h (h = H₂O_mol/O_{mol in oligomer}), was set from 0 to 1.0. The six type conformations with repeated units of O–C, C–C and C–O bonds were examined. Conformational energy, E _c (HF), was calculated as difference between the energy of oligomer with water molecules and that of non-hydrogen and/or hydrogen bonding water molecules. Hydrate energies for each conformer, ∆μ _h (kcal/m.u., based on E _c in non-hydrate state), were negative and linearly decreased with the increase of h values, and such effects with the increase of h values were weaken with increasing x values. These results were consistent with our previous results calculated using the permittivity, ε (ε = 0–80.1), by QCC. In non-hydrate (h = 0), the (ttt) _x conformers were the most stable independent of x. However, in hydrate states (h = 0.44–0.67), the (tg⁺t) _x conformers were the most stable independent of x values, and in h = 1, the (tg⁺t)₈ conformer (8-mer) was most stable [∆E _c(g) = −1.3 kcal/m.u., ∆E _c(g): energy difference between a given oligomer and the (ttt) _x oligomer]. These results supported the experimental those based on NMR analyses using dimethoxyethane and triglyme solutions. Molecular lengths (l) of (tg⁺t) _x , (tg⁺g⁻) _x and (g⁺g⁺g⁺) _x conformers having higher x values significantly decreased with increasing h values. Such contraction with hydration, however, was independent of ΔE _c(g) values of each conformer.