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Entropic Stabilization of Water at Graphitic Interfaces

Pascal, Tod A. and Goddard, William A., III (2021) Entropic Stabilization of Water at Graphitic Interfaces. Journal of Physical Chemistry Letters, 12 (37). pp. 9162-9168. ISSN 1948-7185. doi:10.1021/acs.jpclett.1c02609.

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The thermodynamic stability of water next to graphitic surfaces is of fundamental interest, as it underlies several natural phenomena and important industrial processes. It is commonly assumed that water wets graphite more than graphene due to increased, favorable van der Waals interactions between the interfacial water molecules with multiple carbon sheets. Here, we employed extensive computer simulations and analysis of the molecular correlation functions to show that the interfacial water thermodynamics is in fact dominated by surface entropy. We show that on graphite, destabilization of the interfacial hydrogen bond network leads to an overcompensating increase in population of low frequency translational and librational modes, which is ultimately responsible for the increased interfacial stability compared to graphene. The spectroscopic signature of this effect is an enhancement of the modes near 100 and 300 cm⁻¹. This subtle interplay between entropy and surface binding may have important consideration for interpretations of various phenomena, including the hydrophobic effect.

Item Type:Article
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URLURL TypeDescription
Pascal, Tod A.0000-0003-2096-1143
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2021 American Chemical Society. Received: August 9, 2021; Published: September 15, 2021. This work was initiated with funds from Dow Chemical Corporation (Willie Lau and Joe Rokowski) and NSF (CBET-1067848, George Antos). It was completed with funding from NSF (CBET-1805022, Robert McCabe Pgm Mgr.) (W.A.G.) and funding from NSF (T.A.P.) through the UC San Diego Materials Research Science and Engineering Center (UCSD MRSEC), DMR-2011924. T.A.P. acknowledges the start-up fund from the Jacob School of Engineering at the University of California, San Diego (UCSD). Portions of this work was completed as a user project at the Molecular Foundry, a U.S. Department of Energy Nanoscience Facility at Lawrence Berkeley National Laboratory supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. DOE under Contract No. DE-AC02-05CH11231. Some simulations used resources of the National Energy Research Scientific Computing Center, specifically allocation m3047, which is supported by the Office of Science of the U.S. Department of Energy under the same contract. This work also used the Extreme Science and Engineering Discovery Environment (XSEDE) and the CSD626 allocation on the Comet supercomputer at the San Diego Supercomputing Center, which is supported by National Science Foundation Grant Number ACI-1548562. The authors declare no competing financial interest.
Funding AgencyGrant Number
Dow Chemical CompanyUNSPECIFIED
University of California, San DiegoUNSPECIFIED
Department of Energy (DOE)DE-AC02-05CH11231
Subject Keywords:Entropy, Layers, Carbon, Two dimensional materials, Anode material
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Issue or Number:37
Record Number:CaltechAUTHORS:20210917-215613543
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Official Citation:Entropic Stabilization of Water at Graphitic Interfaces. Tod A. Pascal and William A. Goddard. The Journal of Physical Chemistry Letters 2021 12 (37), 9162-9168; DOI: 10.1021/acs.jpclett.1c02609
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110947
Deposited By: George Porter
Deposited On:20 Sep 2021 14:42
Last Modified:19 Oct 2021 19:04

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