Abstract
Electrophilicity index (𝜔) is related to the energy lowering associated with a maximum amount of electron flow between a donor and an acceptor and possesses adequate information regarding structure, stability, reactivity and interactions. Chemical potential (μ) measures charge transfer from a system to another having a lower value of μ, while chemical hardness (η) is a measure of characterizing relative stability of clusters. The main purpose of the present research work is to examine the Spin-Orbit Coupling (SOC) effect on the behavior of the electrophilicity index, chemical potential, hardness and softness of neutral gold clusters Aun (n=2-6). Using the second-order Douglas-Kroll-Hess Hamiltonian, geometries are optimized at the DKH2-B3P86/DZP-DKH level of theory. Spin-orbit coupling energies are computed using the fourth-order Douglas-Kroll-Hess Hamiltonian, generalized Hartree-Fock method and all-electron relativistic double-ζ level basis set. Then, spin-orbit coupling (SOC) corrections to the electrophilicity index, chemical potential, hardness and softness are calculated. It is revealed that spin-orbit correction to the vertical chemical hardness has important effect on Au3 and Au6, i.e. SOC decreases (increases) the hardness of gold trimer (hexamer). Due to the relationship between hardness and softness, σ = , inclusion of spin-orbit coupling increases (decreases) the softness of Au3 (Au6) and thus destabilizes (stabilizes) it. Spin-orbit coupling (SOC) also has more important effect on the chemical potential of Au3 by decreasing its value. It is found that spin-orbit coupling has considerable effect on the electrophilicity index of gold trimer and greatly increases its value. Furthermore, SOC increases the maximal charge acceptance of Au3 more and thus destabilizes it more. As a result, spin-orbit coupling effect appears to be important in calculating the electrophilicity index of the gold trimer. Doi: 10.28991/HIJ-2021-02-01-05 Full Text: PDF
Highlights
As a kind of promising nanomaterials, metal nanoclusters (NCs) have sparked wide-spread attention
There exist theoretical studies regarding spin-orbit coupling effect using effective core potentials or plane-wave basis sets [13,14,15,16,17,18,19]. These studies mainly focused on the spin-orbit coupling effect on the highest-occupied lowest-unoccupied (HOMO-LUMO) energy gaps, geometries, binding energies per atom and optical absorption of gold clusters
Using the second-order Douglas-Kroll-Hess Hamiltonian, all geometries are fully optimized at the DKH2-B3P86/DZP-DKH level of theory followed by harmonic vibrational frequency analysis
Summary
As a kind of promising nanomaterials, metal nanoclusters (NCs) have sparked wide-spread attention. AuNPs are one of the most promising catalysts, in spite of bulk Au as an inactive material [6,7,8]. There exist theoretical studies regarding spin-orbit coupling effect using effective core potentials or plane-wave basis sets [13,14,15,16,17,18,19]. These studies mainly focused on the spin-orbit coupling effect on the highest-occupied lowest-unoccupied (HOMO-LUMO) energy gaps, geometries, binding energies per atom and optical absorption of gold clusters. Xiao and Wang [13] using
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