Influence of Structural Fluctuations, Proton Transfer, and Electric Field on Polarization Switching of Supported Two-Dimensional Hydrogen-Bonded Oxocarbon Monolayers

Shuang Chen, Axel Enders, Xiao Cheng Zeng

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6 Citations (Scopus)

Abstract

The structural alignment, proton transfer, and molecular dipole under an electric field and as a function of simulation time have been investigated computationally for experimentally observed two-dimensional sheets of croconic acid (CA) on Ag(111) surface and rhodizonic acid (RA) molecules on Au(111) surface at room temperature. Depending on their local environment, some of the OH···O bonds in the CA monolayer exhibit spontaneous proton transfer especially for those bonds that are part of a trimer unit within the hydrogen-bonding network. In stark contrast, the RA molecules exhibit little proton transfer. It is found that thermal structural fluctuations of the molecular layers translate into considerable fluctuations of the polarization vector within the film plane, and even polarization reversal, at room temperature, which even can mask additional contributions to the polarization from the spontaneous and electric field induced proton transfer in CA monolayer. A common feature for both supported CA and RA monolayers is their constant polarization normal to the film plane. (Figure Presented).

Original languageEnglish (US)
Pages (from-to)4839-4847
Number of pages9
JournalChemistry of Materials
Volume27
Issue number13
DOIs
StatePublished - Jul 14 2015

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Proton transfer
Hydrogen
Monolayers
Electric fields
Polarization
Acids
Molecules
Masks
Hydrogen bonds
Temperature
rhodizonic acid

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

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title = "Influence of Structural Fluctuations, Proton Transfer, and Electric Field on Polarization Switching of Supported Two-Dimensional Hydrogen-Bonded Oxocarbon Monolayers",
abstract = "The structural alignment, proton transfer, and molecular dipole under an electric field and as a function of simulation time have been investigated computationally for experimentally observed two-dimensional sheets of croconic acid (CA) on Ag(111) surface and rhodizonic acid (RA) molecules on Au(111) surface at room temperature. Depending on their local environment, some of the OH···O bonds in the CA monolayer exhibit spontaneous proton transfer especially for those bonds that are part of a trimer unit within the hydrogen-bonding network. In stark contrast, the RA molecules exhibit little proton transfer. It is found that thermal structural fluctuations of the molecular layers translate into considerable fluctuations of the polarization vector within the film plane, and even polarization reversal, at room temperature, which even can mask additional contributions to the polarization from the spontaneous and electric field induced proton transfer in CA monolayer. A common feature for both supported CA and RA monolayers is their constant polarization normal to the film plane. (Figure Presented).",
author = "Shuang Chen and Axel Enders and Zeng, {Xiao Cheng}",
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T1 - Influence of Structural Fluctuations, Proton Transfer, and Electric Field on Polarization Switching of Supported Two-Dimensional Hydrogen-Bonded Oxocarbon Monolayers

AU - Chen, Shuang

AU - Enders, Axel

AU - Zeng, Xiao Cheng

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Y1 - 2015/7/14

N2 - The structural alignment, proton transfer, and molecular dipole under an electric field and as a function of simulation time have been investigated computationally for experimentally observed two-dimensional sheets of croconic acid (CA) on Ag(111) surface and rhodizonic acid (RA) molecules on Au(111) surface at room temperature. Depending on their local environment, some of the OH···O bonds in the CA monolayer exhibit spontaneous proton transfer especially for those bonds that are part of a trimer unit within the hydrogen-bonding network. In stark contrast, the RA molecules exhibit little proton transfer. It is found that thermal structural fluctuations of the molecular layers translate into considerable fluctuations of the polarization vector within the film plane, and even polarization reversal, at room temperature, which even can mask additional contributions to the polarization from the spontaneous and electric field induced proton transfer in CA monolayer. A common feature for both supported CA and RA monolayers is their constant polarization normal to the film plane. (Figure Presented).

AB - The structural alignment, proton transfer, and molecular dipole under an electric field and as a function of simulation time have been investigated computationally for experimentally observed two-dimensional sheets of croconic acid (CA) on Ag(111) surface and rhodizonic acid (RA) molecules on Au(111) surface at room temperature. Depending on their local environment, some of the OH···O bonds in the CA monolayer exhibit spontaneous proton transfer especially for those bonds that are part of a trimer unit within the hydrogen-bonding network. In stark contrast, the RA molecules exhibit little proton transfer. It is found that thermal structural fluctuations of the molecular layers translate into considerable fluctuations of the polarization vector within the film plane, and even polarization reversal, at room temperature, which even can mask additional contributions to the polarization from the spontaneous and electric field induced proton transfer in CA monolayer. A common feature for both supported CA and RA monolayers is their constant polarization normal to the film plane. (Figure Presented).

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