Surface Phases and Surface Freezing in an Ionic Liquid

Pontoni, Diego; Haddad, Julia; Murphy, Bridget M.; Festersen, Sven; Konovalov, Oleg; Ocko, Benjamin M.; Deutsch, Moshe

doi:10.1021/acs.jpcc.9b00286

Title: Surface Phases and Surface Freezing in an Ionic Liquid

Journal Article · 15 January 2019 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.9b00286 · OSTI ID:1502805

Pontoni, Diego ^[1]; Haddad, Julia ^[2];

^[3]; Festersen, Sven ^[3]; Konovalov, Oleg ^[1]; Ocko, Benjamin M. ^[4];

^[2]

European Synchrotron Radiation Facility (ESRF), Grenoble (France)
Bar-Ilan Univ., Ramat Gan (Israel)
Univ. of Kiel, Kiel (Germany)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Room temperature ionic liquids (RTILs), a novel class of liquid salts, are intensively studied for their basic science and numerous emerging applications. When undercooled, RTILs comprising long alkyl chains often exhibit liquid crystal (LC) bulk phases. However, only one molecular-resolution experimental structure study was published for their LC surface phases. With this being said, we measured the temperature evolution of another LC surface phase, using surface specific Å-resolution X-ray methods. This phase’s existence range, 90 °C, much exceeds the corresponding bulk phase’s 3 °C. Its thickness, L, confirms the theory-predicted logarithmic temperature dependence, with an amplitude equaling the bulk correlation length. Surprisingly, at L’s divergence temperature, a ~20 Å thick, hexagonally packed, crystalline monolayer forms at, and fully covers, the sample’s surface. Consequently, it is identified as a surface-frozen Langmuir–Gibbs film and fundamentally differs from the only reported RTIL surface crystal, a Coulomb-dominated, four-layer, island phase, covering only 5%–15% of the surface.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1502805

Report Number(s):: BNL--211433-2019-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 5 Vol. 123; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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