Ab InitioMolecular Dynamics Study of Methanol-Water Mixtures under External Electric Fields

0537805 - BFÚ 2021 RIV CH eng J - Článek v odborném periodiku
Cassone, G. - Sofia, A. - Šponer, Jiří - Saitta, A. M. - Saija, F.
Ab InitioMolecular Dynamics Study of Methanol-Water Mixtures under External Electric Fields.
Molecules. Roč. 25, č. 15 (2020), č. článku 3371. E-ISSN 1420-3049
Institucionální podpora: RVO:68081707
Klíčová slova: molecular-dynamics * liquid water * density * simulations * polarization * diffusion
Obor OECD: Biochemistry and molecular biology
Impakt faktor: 4.412, rok: 2020
Způsob publikování: Open access
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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-artab initiomolecular 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.
Trvalý link: http://hdl.handle.net/11104/0315642