Molecular dissociation and proton transfer in aqueous methane solution under an electric field

0554408 - BFÚ 2022 RIV GB eng J - Článek v odborném periodiku
Cassone, G. - Šponer, Jiří - Saija, F.
Molecular dissociation and proton transfer in aqueous methane solution under an electric field.
Physical Chemistry Chemical Physics. Roč. 23, č. 45 (2021), s. 25649-25657. ISSN 1463-9076. E-ISSN 1463-9084
Institucionální podpora: RVO:68081707
Klíčová slova: functional theory * liquid water * dynamics * polarization * fluctuations * catalysis
Obor OECD: Physical chemistry
Impakt faktor: 3.945, rok: 2021
Způsob publikování: Open access s časovým embargem
https://pubs.rsc.org/en/content/articlelanding/2021/CP/D1CP04202E

Methane-water mixtures are ubiquitous in our solar system and they have been the subject of a wide variety of experimental, theoretical, and computational studies aimed at understanding their behaviour under disparate thermodynamic scenarios, up to extreme planetary ice conditions of pressures and temperatures [Lee and Scandolo, Nat. Commun., 2011, 2, 185]. Although it is well known that electric fields, by interacting with condensed matter, can produce a range of catalytic effects which can be similar to those observed when material systems are pressurised, to the best of our knowledge, no quantum-based computational investigations of methane-water mixtures under an electric field have been reported so far. Here we present a study relying upon state-of-the-art ab initio molecular dynamics simulations where a liquid aqueous methane solution is exposed to strong oriented static and homogeneous electric fields. It turns out that a series of field-induced effects on the dipoles, polarisation, and the electronic structure of both methane and water molecules are recorded. Moreover, upon increasing the field strength, increasing fractions of water molecules are not only re-oriented towards the field direction, but are also dissociated by the field, leading to the release of oxonium and hydroxyde ions in the mixture. However, in contrast to what is observed upon pressurisation (similar to 50 GPa), where the presence of the water counterions triggers methane ionisation and other reactions, methane molecules preserve their integrity up to the strongest field explored (i.e., 0.50 V angstrom(-1)). Interestingly, neither the field-induced molecular dissociation of neat water (i.e., 0.30 V angstrom(-1)) nor the proton conductivity typical of pure aqueous samples at these field regimes (i.e., 1.3 S cm(-1)) are affected by the presence of hydrophobic interactions, at least in a methane-water mixture containing a molar fraction of 40% methane.
Trvalý link: http://hdl.handle.net/11104/0329106