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Title: Silver clusters tune up electronic properties of graphene nanoflakes: A comprehensive theoretical study

Abstract

Graphene-silver composites reflect a synergic effect of both components with enhanced electronic, adsorption and catalytic properties. We introduce here the detailed theoretical study on geometric, thermodynamic and electronic properties of silver clusters Agn (n=2–10) adsorbed on graphene nanoflakes as a model for silver-graphene composites. First, a benchmark study is performed on Agn…coronene complexes (n=2, 4) by evaluating various functional against reported high level ab-initio method for the selection of best functional for further calculations. Then, density functional theory study at the best chosen level is performed to inquire how clustering of adsorbate attached with carbon surface can impact geometric, electronic and thermodynamic properties of silver-graphene composites. Furthermore, the interaction energies are corrected for dispersion and basis set superposition error in order to get more realistic estimate of interaction energies. In progression, we investigated the dependence of interaction energy upon cluster size and dimensionality. For Agn…coronene, the binding energies increase monotonically as the number of atoms in the cluster increases. However, for Agn…dodecabenzocoronene, the interaction energies show a sudden drop at Ag7…dodecabenzocoronene. The difference in behavior between Agn…dodecabenzocoronene and Agn…coronene for interaction energy is attributed to edge effect present in coronene. Furthermore, coplanar orientations of the silver clusters on polyaromatic hydrocarbonsmore » have higher interaction energies. The 2D-3D transition of the silver cluster is observed for Ag7…coronene. CDA analysis reveals that backdonation from dodecabenzocoronene to silver clusters is more dominant in Ag4–Ag7 whereas other clusters have dominant charge transfer to dodecabenzocoronene. Charge transfer analysis via constrained density functional theory (CDFT) reveals significant energy lowering from charge donor-acceptor interactions. Further energy decomposition analysis (EDA) using absolutely-localized molecular orbitals (ALMO) suggests that, while charge-transfer is important in these systems, the sum of electrostatics, Pauli repulsion, and London dispersion are far more significant as silver cluster size increases. NCI results also support the presence of van der Waals and electrostatic interactions. The hollow top is most favorite interaction sites compared to bridge top and head top binding sites over coronene lattice. The ionization potential, electron affinity, frontier molecular orbital analysis, chemical hardness, softness, chemical potential, and Fermi levels are deliberated to verify the stability and reactivity of most stable silver-graphene composites. The remarkable outcome of the current findings makes our silver-graphene composite as a potential applicant for high performance electronic and catalytic devices.« less

Authors:
 [1];  [2];  [3];  [2];  [4];  [3];  [5];  [1]
  1. COMSATS Univ. Islamabad-Abbottabad Campus (Pakistan)
  2. The Ohio State Univ., Columbus, OH (United States)
  3. Government College Univ., Lahore (Pakistan)
  4. Univ. of Okara (Pakistan)
  5. Univ. of Agriculture, Faisalabad (Pakistan)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1604440
Alternate Identifier(s):
OSTI ID: 1691705
Grant/Contract Number:  
SC0008850; SC0008550
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Molecular Liquids
Additional Journal Information:
Journal Volume: 297; Journal Issue: C; Journal ID: ISSN 0167-7322
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Silver-graphene composites; Surface interaction; Density functional theory; Electronic properties

Citation Formats

Jadoon, Tabish, Carter-Fenk, Kevin, Siddique, Muhammad Bilal Ahmed, Herbert, John M., Hussain, Riaz, Iqbal, Sarosh, Iqbal, Javed, and Ayub, Khurshid. Silver clusters tune up electronic properties of graphene nanoflakes: A comprehensive theoretical study. United States: N. p., 2019. Web. doi:10.1016/j.molliq.2019.111902.
Jadoon, Tabish, Carter-Fenk, Kevin, Siddique, Muhammad Bilal Ahmed, Herbert, John M., Hussain, Riaz, Iqbal, Sarosh, Iqbal, Javed, & Ayub, Khurshid. Silver clusters tune up electronic properties of graphene nanoflakes: A comprehensive theoretical study. United States. https://doi.org/10.1016/j.molliq.2019.111902
Jadoon, Tabish, Carter-Fenk, Kevin, Siddique, Muhammad Bilal Ahmed, Herbert, John M., Hussain, Riaz, Iqbal, Sarosh, Iqbal, Javed, and Ayub, Khurshid. Wed . "Silver clusters tune up electronic properties of graphene nanoflakes: A comprehensive theoretical study". United States. https://doi.org/10.1016/j.molliq.2019.111902. https://www.osti.gov/servlets/purl/1604440.
@article{osti_1604440,
title = {Silver clusters tune up electronic properties of graphene nanoflakes: A comprehensive theoretical study},
author = {Jadoon, Tabish and Carter-Fenk, Kevin and Siddique, Muhammad Bilal Ahmed and Herbert, John M. and Hussain, Riaz and Iqbal, Sarosh and Iqbal, Javed and Ayub, Khurshid},
abstractNote = {Graphene-silver composites reflect a synergic effect of both components with enhanced electronic, adsorption and catalytic properties. We introduce here the detailed theoretical study on geometric, thermodynamic and electronic properties of silver clusters Agn (n=2–10) adsorbed on graphene nanoflakes as a model for silver-graphene composites. First, a benchmark study is performed on Agn…coronene complexes (n=2, 4) by evaluating various functional against reported high level ab-initio method for the selection of best functional for further calculations. Then, density functional theory study at the best chosen level is performed to inquire how clustering of adsorbate attached with carbon surface can impact geometric, electronic and thermodynamic properties of silver-graphene composites. Furthermore, the interaction energies are corrected for dispersion and basis set superposition error in order to get more realistic estimate of interaction energies. In progression, we investigated the dependence of interaction energy upon cluster size and dimensionality. For Agn…coronene, the binding energies increase monotonically as the number of atoms in the cluster increases. However, for Agn…dodecabenzocoronene, the interaction energies show a sudden drop at Ag7…dodecabenzocoronene. The difference in behavior between Agn…dodecabenzocoronene and Agn…coronene for interaction energy is attributed to edge effect present in coronene. Furthermore, coplanar orientations of the silver clusters on polyaromatic hydrocarbons have higher interaction energies. The 2D-3D transition of the silver cluster is observed for Ag7…coronene. CDA analysis reveals that backdonation from dodecabenzocoronene to silver clusters is more dominant in Ag4–Ag7 whereas other clusters have dominant charge transfer to dodecabenzocoronene. Charge transfer analysis via constrained density functional theory (CDFT) reveals significant energy lowering from charge donor-acceptor interactions. Further energy decomposition analysis (EDA) using absolutely-localized molecular orbitals (ALMO) suggests that, while charge-transfer is important in these systems, the sum of electrostatics, Pauli repulsion, and London dispersion are far more significant as silver cluster size increases. NCI results also support the presence of van der Waals and electrostatic interactions. The hollow top is most favorite interaction sites compared to bridge top and head top binding sites over coronene lattice. The ionization potential, electron affinity, frontier molecular orbital analysis, chemical hardness, softness, chemical potential, and Fermi levels are deliberated to verify the stability and reactivity of most stable silver-graphene composites. The remarkable outcome of the current findings makes our silver-graphene composite as a potential applicant for high performance electronic and catalytic devices.},
doi = {10.1016/j.molliq.2019.111902},
journal = {Journal of Molecular Liquids},
number = C,
volume = 297,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: Interaction energy (kcal mol-1) of most stable Agn…coronene (n=2-10) composites.

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