Single Particle Dynamics at the Intrinsic Surface of Various Apolar, Aprotic Dipolar, and Hydrogen Bonding Liquids As Seen from Computer Simulations

Author(s)
Balazs Fabian, Marcello Sega, George Horvai, Pal Jedlovszky
Abstract

We investigate the single molecule dynamics at the intrinsic liquid/vapor interface of five different molecular liquids (carbon tetrachloride, acetone, acetonitrile, methanol, and water). After assessing that the characteristic residence times in the surface layer are long enough for a meaningful definition of several transport properties within the layer itself, we characterize the dynamics of the individual molecules at the liquid surface by analyzing their normal and lateral mean-square displacements and lateral velocity autocorrelation functions and, in the case of the hydrogen bonding liquids (i.e., water and methanol), also the properties of the hydrogen bonds. Further, dynamical properties as well as the clustering of the molecules residing unusually long in the surface layer are also investigated. The global picture emerging from this analysis is that of a noticeably enhanced dynamics of the molecules at the liquid surface, with diffusion coefficients up to 4 times larger than in the bulk, and the disappearance of the caging effect at the surface of all liquids but water. The dynamics of water is dominated by the strong hydrogen bonding structure also at the liquid surface.

Organisation(s)
Computational and Soft Matter Physics
External organisation(s)
Budapest University of Technology and Economics, Université de Franche-Comté, Eszterházy Károly University of Applied Sciences
Journal
The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Volume
121
Pages
5582-5594
No. of pages
13
ISSN
1520-6106
DOI
https://doi.org/10.1021/acs.jpcb.7b02220
Publication date
06-2017
Peer reviewed
Yes
Austrian Fields of Science 2012
104026 Spectroscopy, 103015 Condensed matter, 104002 Analytical chemistry
Keywords
ASJC Scopus subject areas
Materials Chemistry, Surfaces, Coatings and Films, Physical and Theoretical Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/163d5ec3-d0a1-415f-bfe8-848304c8574d