Ab initio molecular dynamics studies of formic acid dimer colliding with liquid water

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.author Hänninen, Vesa
dc.contributor.author Murdachaew, Garold
dc.contributor.author Nathanson, Gilbert M.
dc.contributor.author Gerber, R. Benny
dc.contributor.author Halonen, Lauri
dc.date.accessioned 2018-10-16T08:53:46Z
dc.date.available 2018-10-16T08:53:46Z
dc.date.issued 2018-01-01
dc.identifier.citation Hänninen , V , Murdachaew , G , Nathanson , G M , Gerber , R B & Halonen , L 2018 , ' Ab initio molecular dynamics studies of formic acid dimer colliding with liquid water ' Physical Chemistry Chemical Physics , vol 20 , no. 36 , pp. 23717-23725 . DOI: 10.1039/c8cp03857k en
dc.identifier.issn 1463-9076
dc.identifier.issn 1463-9084
dc.identifier.other PURE UUID: 2378ed3f-e9a8-4f7d-82af-363e72d50b59
dc.identifier.other PURE ITEMURL: https://research.aalto.fi/en/publications/ab-initio-molecular-dynamics-studies-of-formic-acid-dimer-colliding-with-liquid-water(2378ed3f-e9a8-4f7d-82af-363e72d50b59).html
dc.identifier.other PURE LINK: http://www.scopus.com/inward/record.url?scp=85053775553&partnerID=8YFLogxK
dc.identifier.other PURE FILEURL: https://research.aalto.fi/files/28561684/CHEM_H_nninen_et_al_Ab_initio_molecular_dynamics_2018_Physical_Chemistry_Chemical_Physics.pdf
dc.identifier.uri https://aaltodoc.aalto.fi/handle/123456789/34263
dc.description.abstract Ab initio molecular dynamics simulations of formic acid (FA) dimer colliding with liquid water at 300 K have been performed using density functional theory. The two energetically lowest FA dimer isomers were collided with a water slab at thermal and high kinetic energies up to 68kBT. Our simulations agree with recent experimental observations of nearly a complete uptake of gas-phase FA dimer: the calculated average kinetic energy of the dimers immediately after collision is 5 ± 4% of the incoming kinetic energy, which compares well with the experimental value of 10%. Simulations support the experimental observation of no delayed desorption of FA dimers following initial adsorption. Our analysis shows that the FA dimer forms hydrogen bonds with surface water molecules, where the hydrogen bond order depends on the dimer structure, such that the most stable isomer possesses fewer FA-water hydrogen bonds than the higher energy isomer. Nevertheless, even the most stable isomer can attach to the surface through onehydrogen bond despite its reduced hydrophilicity. Our simulations further show that the probability of FA dimer dissociation is increased by high collision energies, the dimer undergoes isomerization from the higher energy to the lowest energy isomer, and concerted double-proton transfer occurs between the FA monomers. Interestingly, proton transfer appears to be driven by the release of energy arising from such isomerization, which stimulates those internal vibrational degrees of freedom that overcome the barrier of a proton transfer. en
dc.format.extent 9
dc.format.extent 23717-23725
dc.format.mimetype application/pdf
dc.language.iso en en
dc.relation.ispartofseries Physical Chemistry Chemical Physics en
dc.relation.ispartofseries Volume 20, issue 36 en
dc.rights openAccess en
dc.subject.other Physics and Astronomy(all) en
dc.subject.other Physical and Theoretical Chemistry en
dc.subject.other 116 Chemical sciences en
dc.title Ab initio molecular dynamics studies of formic acid dimer colliding with liquid water en
dc.type A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä fi
dc.description.version Peer reviewed en
dc.contributor.department University of Helsinki
dc.contributor.department Department of Chemistry and Materials Science
dc.contributor.department University of Wisconsin-Madison
dc.contributor.department Hebrew University of Jerusalem
dc.subject.keyword Physics and Astronomy(all)
dc.subject.keyword Physical and Theoretical Chemistry
dc.subject.keyword 116 Chemical sciences
dc.identifier.urn URN:NBN:fi:aalto-201810165340
dc.identifier.doi 10.1039/c8cp03857k
dc.type.version publishedVersion

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