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

Wang, Yong; Ren, Fangfang; Cao, Duanlin

doi:10.1007/s00894-019-4216-z

Cited by 8 publications

(6 citation statements)

References 75 publications

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“…In general, the change of the barrier compared with that in no field is no more than 15.0 kJ/mol with the field strength of −0.010 or +0.010 a.u. [34][35][36]52]. The changes of the barriers induced by the external electric fields are also reflected in the imaginary vibrations, Gibbs energies and rate constants.…”

Section: Concerted Effect Of Intermolecular Hydrogen Exchange In Exte...mentioning

confidence: 99%

Strong External Electric Fields Reduce Explosive Sensitivity. A Theoretical Investigation Into the Reaction Selectivity in NH2NO2···NH3

Ren¹,

Liu²,

Wang³

et al. 2023

Preprint

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Controlling the selectivity of detonation initiation reaction of explosive is a Holy Grail, and it seems to be an “idiot's daydream”, by strengthening external electric field, to reduce the explosive sensitivity. The effects of external electric fields on the initiation reactions in NH2NO2∙∙∙NH3, a model system of the nitroamine explosive with alkaline additive, were investigated at the MP2/6-311++G(2d,p) and CCSD/6-311++G(2d,p) level. The concerted effect in the intermolecular hydrogen exchange is characterized by an index of the imaginary vibrations. Due to the weakened concerted effects by the electric field along the −x-direction opposite to the “reaction axis”, the dominant reaction changes from the hydrogen exchange to 1,3-intramolecular hydrogen transference with the increase of the field strengths. Furthermore, the stronger the field strengths, the higher the barrier heights become, indicating the lower sensitivities. Therefore, by strengthening the field strength and adjusting the orientation between the field and “reaction axis”, not only can the reaction selectivity be controlled, but also the sensitivity can be reduced, in particular under a super-strong field. Thus, a traditional concept, which the explosive is dangerous under the super-strong external electric field, is broken theoretically. Compared to the neutral medium, the low sensitivity of the explosive with alkaline can be achieved under the stronger field. Employing atoms in molecules, reduced density gradient and surface electrostatic potentials, the origin of the reaction selectivity and sensitivity change is revealed. This work provides a new idea to the technical improvement for adding the external electric field into the explosive system.

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Section: Concerted Effect Of Intermolecular Hydrogen Exchange In Exte...mentioning

confidence: 99%

Strong External Electric Fields Reduce Explosive Sensitivity. A Theoretical Investigation Into the Reaction Selectivity in NH2NO2···NH3

Ren¹,

Liu²,

Wang³

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…EEFs alter molecular reactivity by triggering charge separation such that the molecular dipole moment is maximized along the field direction and hence a reorganization of electron density as well as relaxation of the molecular structure. This phenomenon can lead to a range of effects: alterations of the relative stability of tautomers, , changes in absorption bands, , and modifications of various electronic properties , (conductor-to-insulator transitions and vice versa, etc.) in the presence of EEFs.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of the X-ray Stark Effect in Small Molecules

2023

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We have studied the Stark effect in the soft x-ray region for various small molecules by calculating the fielddependent x-ray absorption spectra. This effect is explained in terms of the response of molecular orbitals (core and valence), the molecular dipole moment, and the molecular geometry to the applied electric field. A number of consistent trends are observed linking the computed shifts in absorption energies and intensities with specific features of the molecular electronic structure. We find that both the virtual molecular orbitals (valence and/or Rydberg) as well as the core orbitals contribute to observed trends in a complementary fashion. This initial study highlights the potential impact of x-ray Stark spectroscopy as a tool to study electronic structure and environmental perturbations at a submolecular scale.

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“…An electromagnetic pulse effect was tested during the bridge wire electric explosion [ 2 ]. We have found that, for the simple (pure) explosives, the bond dissociation energies (BDEs) of the “trigger linkages” and barrier heights of the initiation reactions could be increased under certain external electric fields, and the selectivity of the detonation initiation reaction could be controlled, and thus the explosive sensitivities were reduced by the adjustment of the strength or orientation of the external electric fields [ 34 , 35 , 36 ]. For the mixture of nitroamine explosive with H 2 O, NH 2 NO 2 ∙∙∙H 2 O as a model system, an abrupt jump of the activation energy between the intermolecular and 1,3-intramolecular hydrogen transfer reactions was confirmed.…”

Section: Introductionmentioning

confidence: 99%

Strong External Electric Fields Reduce Explosive Sensitivity: A Theoretical Investigation into the Reaction Selectivity in NH2NO2∙∙∙NH3

Ren

Liu²,

Wang

et al. 2023

Molecules

Self Cite

View full text Add to dashboard Cite

Controlling the selectivity of a detonation initiation reaction of explosive is essential to reduce sensitivity, and it seems impossible to reduce it by strengthening the external electric field. To verify this, the effects of external electric fields on the initiation reactions in NH2NO2∙∙∙NH3, a model system of the nitroamine explosive with alkaline additive, were investigated at the MP2/6-311++G(2d,p) and CCSD(T)/6-311++G(2d,p) levels. The concerted effect in the intermolecular hydrogen exchange is characterized by an index of the imaginary vibrations. Due to the weakened concerted effects by the electric field along the −x-direction opposite to the “reaction axis”, the dominant reaction changes from the intermolecular hydrogen exchange to 1,3-intramolecular hydrogen transference with the increase in the field strengths. Furthermore, the stronger the field strengths, the higher the barrier heights become, indicating the lower sensitivities. Therefore, by increasing the field strength and adjusting the orientation between the field and “reaction axis”, not only can the reaction selectivity be controlled, but the sensitivity can also be reduced, in particular under a super-strong field. Thus, a traditional concept, in which the explosive is dangerous under the super-strong external electric field, is theoretically broken. Compared to the neutral medium, a low sensitivity of the explosive with alkaline can be achieved under the stronger field. Employing atoms in molecules, reduced density gradient, and surface electrostatic potentials, the origin of the reaction selectivity and sensitivity change is revealed. This work provides a new idea for the technical improvement regarding adding the external electric field into the explosive system.

show abstract

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

Cited by 8 publications

References 75 publications

Strong External Electric Fields Reduce Explosive Sensitivity. A Theoretical Investigation Into the Reaction Selectivity in NH2NO2···NH3

Strong External Electric Fields Reduce Explosive Sensitivity. A Theoretical Investigation Into the Reaction Selectivity in NH2NO2···NH3

Theoretical Investigation of the X-ray Stark Effect in Small Molecules

Strong External Electric Fields Reduce Explosive Sensitivity: A Theoretical Investigation into the Reaction Selectivity in NH2NO2∙∙∙NH3

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