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Title: Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers

According to recent experiments, atomically thin hexagonal boron nitride and graphene are permeable to protons and deuterons (and not to other atomic species), and the experimental estimates of the activation energy are lower than the theoretical values by about 0.5 eV for the isolated proton-membrane transfer model. Our analysis of the electronic potential energy surfaces along the normal to the transmission direction, obtained using correlated electronic structure methods, suggests that the aqueous environment is essential to stabilize the proton { as opposed to the hydrogenatom { transmission. Therefore, the process is examined within a molecular model of H 2O { H(D) + { material { H 2O. Exact quantum-mechanical scattering calculations are performed to assess the relevance of the nuclear quantum eects, such as tunneling factors and the kinetic isotope eect (KIE). Deuteration is found to aect the thermal reaction rate constants (KIE of 3-4 for hexagonal boron nitride and 20-30 for the graphene) and to eectively lower the barriers to the proton transfer by 0.2 and 0.4 eV for the two membranes, respectively. This lowering eect is reduced for the deuteron by approximately a factor of three. A more comprehensive description of the proton transmission is likely to requiremore » an extended explicit aqueous environment.« less
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 43; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1427695

Ekanayake, Niranji, Huang, Jingsong, Jakowski, Jacek, Sumpter, Bobby G., and Garashchuk, Sofiya V.. Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers. United States: N. p., Web. doi:10.1021/acs.jpcc.7b08152.
Ekanayake, Niranji, Huang, Jingsong, Jakowski, Jacek, Sumpter, Bobby G., & Garashchuk, Sofiya V.. Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers. United States. doi:10.1021/acs.jpcc.7b08152.
Ekanayake, Niranji, Huang, Jingsong, Jakowski, Jacek, Sumpter, Bobby G., and Garashchuk, Sofiya V.. 2017. "Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers". United States. doi:10.1021/acs.jpcc.7b08152. https://www.osti.gov/servlets/purl/1427695.
@article{osti_1427695,
title = {Relevance of the Nuclear Quantum Effects on the Proton/Deuteron Transmission through Hexagonal Boron Nitride and Graphene Monolayers},
author = {Ekanayake, Niranji and Huang, Jingsong and Jakowski, Jacek and Sumpter, Bobby G. and Garashchuk, Sofiya V.},
abstractNote = {According to recent experiments, atomically thin hexagonal boron nitride and graphene are permeable to protons and deuterons (and not to other atomic species), and the experimental estimates of the activation energy are lower than the theoretical values by about 0.5 eV for the isolated proton-membrane transfer model. Our analysis of the electronic potential energy surfaces along the normal to the transmission direction, obtained using correlated electronic structure methods, suggests that the aqueous environment is essential to stabilize the proton { as opposed to the hydrogenatom { transmission. Therefore, the process is examined within a molecular model of H2O { H(D)+ { material { H2O. Exact quantum-mechanical scattering calculations are performed to assess the relevance of the nuclear quantum eects, such as tunneling factors and the kinetic isotope eect (KIE). Deuteration is found to aect the thermal reaction rate constants (KIE of 3-4 for hexagonal boron nitride and 20-30 for the graphene) and to eectively lower the barriers to the proton transfer by 0.2 and 0.4 eV for the two membranes, respectively. This lowering eect is reduced for the deuteron by approximately a factor of three. A more comprehensive description of the proton transmission is likely to require an extended explicit aqueous environment.},
doi = {10.1021/acs.jpcc.7b08152},
journal = {Journal of Physical Chemistry. C},
number = 43,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}