Journal of Molecular Modeling

, 25:330 | Cite as

A dynamic and electrostatic potential prediction of the prototropic tautomerism between imidazole 3-oxide and 1-hydroxyimidazole in external electric field

  • Yong Wang
  • Fu-de RenEmail author
  • Duan-lin Cao
Original Paper


In order to obtain an optimum scheme for separating the proton-transfer tautomer, a dynamic investigation into the effect of the external electric field on the proton-transfer tautomeric conversion in imidazole 3-oxide and 1-hydroxyimidazole was carried out at the M06-2X/6-311++G** and CCSD(T)/6-311++G(2d,p) level, accompanied by the analysis of the surface electrostatic potentials. The results show that, for both the forward reaction “imidazole 3-oxide → N-hydroxyimidazole free radical → 1-hydroxyimidazole” and its reverse reaction processes, the fields parallel to the N→O or N−OH bond axis affect the barrier heights and rate constants considerably more than those parallel to the other orientations. As the field strength is increased along the orientation from the O to N atom, the chemical equilibrium moves toward the direction for the formation of 1-hydroxyimidazole, while the amount of imidazole 3-oxide is increased with the increased field strength along the opposite orientation. In the fields along the orientation consistent with the dipole moment, the electrostatic potentials and their variances “abnormally” increase for the transition states with the N→O bond in comparison with those in no field (they decrease generally), which enhances the nucleophilicity of the coordination O atom and the electrophilicity of the activated H atom. The analyses of the AIM (atoms in molecules) and NICS (nucleus-independent chemical shift) were used to explain the above anomaly.

Graphical Abstract

Electrostatic potentials and their variances “abnormally” increase in the external electric field, which greatly affects tautomeric conversion


Prototropic tautomerism External electric field Dynamics Imidazole 3-oxide Surface Electrostatic potential 


Compliance with ethical standards

Ethics statement

We allow the journal to review all the data, and we confirm the validity of results. There is none of the financial relationships. This work was not published previously and it is not submitted to more than one journal. It is also not split up into several parts to submit. No data have been fabricated or manipulated.

Supplementary material

894_2019_4216_MOESM1_ESM.doc (7.7 mb)
ESM 1 The optimized geometrical parameters and AIM results of TS1 and TS2 in the different field strengths and orientations, as well as the changes in the bond lengths, electron densities, laplacians versus field strengths along the z- or y-direction are collected in Supplementary data. (DOC 7877 kb)


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Authors and Affiliations

  1. 1.School of Chemical Engineering and TechnologyNorth University of ChinaShanxi TaiyuanChina

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