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

Graphene-silver composites show a synergic effect of both components with enhanced electronic, adsorption and catalytic properties. We present here the detailed theoretical study on geometric, thermodynamic and electronic properties of silver clusters Ag-n (n = 2-10) adsorbed on graphene nanoflakes as a model for silver-graphene composites. First, a benchmark study is performed on Ag-n...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 Ag-n...coronene, the binding energies increase monotonically as the number of atoms in the cluster increases. However, for Ag-n... dodecabenzocoronene, the interaction energies show a sudden drop at Ag-n...dodecabenzocoronene. The difference in behavior between Ag-n...dodecabenzocoronene and Ag-n...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 Ag-n... coronene. CDA analysis reveals that backdonation from dodecabenzocoronene to silver clusters is more dominant in Ag-4-Ag-7 whereas other clusters have dominant charge transfer to dodecabenzocoronene. Charge transfer analysis via constrained density functional theory (CDFF) reveals significant energy lowering from charge donoracceptor 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. NCl 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. (C) 2019 Elsevier B.V. All rights reserved.