Ab initio molecular dynamics study of dissociation of water under an electric field

Abstract

The behavior of liquid water under an electric field is a crucial phenomenon in science and engineering. However, its detailed description at a microscopic level is difficult to achieve experimentally. Here we report on the first ab initio molecular-dynamics study on water under an electric field. We observe that the hydrogen-bond length and the molecular orientation are significantly modified at low-to-moderate field intensities. Fields beyond a threshold of about 0.35 V/Åare able to dissociate molecules and sustain an ionic current via a series of correlated proton jumps. Upon applying even more intense fields (1.0 V/Å), a 15-20% fraction of molecules are instantaneously dissociated and the resulting ionic flow yields a conductance of about 7.8 ${\Omega }^{-1}c{m}^{-1}$, in good agreement with experimental values. This result paves the way to quantum-accurate microscopic studies of the effect of electric fields on aqueous solutions and, thus, to massive applications of ab initio molecular dynamics in neurobiology, electrochemistry and hydrogen economy.

5 pages, 4 figures. Supplementary material available upon request. To be published in Phys. Rev. Lett. http://prl.aps.org/accepted/

References in corpus (1)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials

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