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

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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 . https://doi.org/10.1039/c8cp03857k

Title: Ab initio molecular dynamics studies of formic acid dimer colliding with liquid water
Author: Hänninen, Vesa; Murdachaew, Garold; Nathanson, Gilbert M.; Gerber, R. Benny; Halonen, Lauri
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
Date: 2018-09-28
Language: eng
Number of pages: 9
Belongs to series: Physical Chemistry Chemical Physics
ISSN: 1463-9076
URI: http://hdl.handle.net/10138/259421
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 68k(B)T. 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 one hydrogen 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.
Subject: DOUBLE-PROTON-TRANSFER
MONTE-CARLO-SIMULATION
CARBOXYLIC-ACIDS
CONDENSED PHASES
ACETIC-ACID
SOLVENT
SPECTROSCOPY
DIMERIZATION
MECHANISM
SURFACES
116 Chemical sciences
114 Physical sciences
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