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

Ekanayake, Niranji; Huang, Jingsong; Jakowski, Jacek; Sumpter, Bobby G.; Garashchuk, Sofiya V.

doi:10.1021/acs.jpcc.7b08152

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

Journal Article · Mon Oct 02 00:00:00 EDT 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b08152· OSTI ID:1427695

Ekanayake, Niranji ^[1];

^[2];

^[1]

Univ. of South Carolina, Columbia, SC (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1427695

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 43; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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Theoretical assessment of the nuclear quantum effects on polymer crystallinity via perturbation theory and dynamics Jakowski, Jacek; Huang, Jingsong; Sumpter, Bobby G. International Journal of Quantum Chemistry, Vol. 118, Issue 20 https://doi.org/10.1002/qua.25712	journal	September 2018
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