Estimating the Impact of an All-Electron Basis Set and Scalar Relativistic Effects on the Structure, Stability, and Reactivity of Small Copper Clusters

Francisco E Jorge,Danilo D Soprani,Thieberson Gomes,Igor B Ferreira

doi:10.5935/0103-5053.20150261

Francisco E Jorge, Danilo D Soprani + Show 2 more

Open Access

https://doi.org/10.5935/0103-5053.20150261

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Abstract

Basis sets of valence double and quadruple zeta qualities and the Douglas-Kroll-Hess (DKH) approximation are used to estimate the impact of an all-electron basis set and scalar relativistic effects on the structure, stability, and electronic properties of small neutral copper clusters (Cun, n ≤ 8). At the Becke three-parameter for exchange and Perdew-Wang 91 for correlation (B3PW91) non-relativistic and relativistic levels of theory, the bond length, binding energy, ionization potential, electron affinity, chemical potential, chemical hardness, and electrophilicity index are calculated. The results show that the agreement with experiment improves significantly when the DKH Hamiltonian combined with an all-electron relativistic basis set is used. Polarizabilities and hyperpolarizability are also reported. At the B3PW91 level, all-electron basis sets are shown to be more reliable than effective core potential valence basis sets in the determination of the second hyperpolarizability of copper clusters.

Highlights

Atomic and molecular clusters are frequently studied because of their unusual characteristics and properties and encouraging technological applications.[1]
From equations 3 and 4, it is clear that the ionization potential (IP) and electron affinity (EA) are fundamental to obtaining a reliable estimation of chemical potential and hardness
When relativistic effects are included. These results show the importance of using scalar relativistic effects along with an all-electron basis set to obtain reliable copper cluster structures

Summary

Introduction

Atomic and molecular clusters are frequently studied because of their unusual characteristics and properties and encouraging technological applications.[1]. Because clusters represent the precursors of bulk material, knowledge of their properties provides information about the transition from atom or molecule to the solid state. The goal of most studies has been to examine how the properties of a cluster evolve with size. These properties include the geometric structures, binding energies, ionization energies, and the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies

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