Intense electric fields applied on H-bonded systems are able to induce molecular dissociations, proton transfers, and complex chemical reactions. Nevertheless, the effects induced in heterogeneous molecular systems such as methanol-water mixtures are still elusive. Here we report on a series of state-of-the-art ab initio molecular dynamics simulations of liquid methanol-water mixtures at different molar ratios exposed to static electric fields. If, on the one hand, the presence of water increases the proton conductivity of methanol-water mixtures, on the other, it hinders the typical enhancement of the chemical reactivity induced by electric fields. In particular, a sudden increase of the protonic conductivity is recorded when the amount of water exceeds that of methanol in the mixtures, suggesting that important structural changes of the H-bond network occur. By contrast, the field-induced multifaceted chemistry leading to the synthesis of e.g., hydrogen, dimethyl ether, formaldehyde, and methane observed in neat methanol, in 75:25, and equimolar methanol-water mixtures, completely disappears in samples containing an excess of water and in pure water. The presence of water strongly inhibits the chemical reactivity of methanol.

CNR IPCF Viale F Stagno d'Alcontres 37 98158 Messina Italy

Dipartimento di Matematica G Peano Università degli Studi di Torino Via Carlo Alberto 10 10123 Torino Italy

Institute of Biophysics of the Czech Academy of Sciences Královopolská 135 61265 Brno Czech Republic

Sorbonne Université Msuéum National d'Histoire Naturelle UMR CNRS 7590 IMPMC F 075005 Paris France

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