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Updated: Apr 16, 2026

Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Relativistic and Electron-Correlation Effects in Static Dipole Polarizabilities for Group 11 Elements
1Institute of Applied Analysis and Numerical Simulation, University of Stuttgart, Pfaffenwaldring 57, 70569 Stuttgart, Germany.
This study precisely calculates static dipole polarizabilities for copper, silver, and gold using advanced relativistic methods. Results offer improved accuracy and reduced uncertainties for these important elements.
Area of Science:
- Atomic physics and quantum chemistry.
- Computational chemistry and relativistic quantum mechanics.
Background:
- Static dipole polarizability is a crucial property for understanding atomic and molecular responses to electric fields.
- Accurate calculations for group 11 elements (Cu, Ag, Au) are essential due to their unique electronic structures and relativistic effects.
Purpose of the Study:
- To compute highly accurate static dipole polarizabilities for neutral Cu, Ag, and Au.
- To investigate and quantify the impact of various relativistic effects (scalar-relativistic, spin-orbit coupling) on these polarizabilities.
- To provide recommended values with reduced uncertainties compared to existing literature.
Main Methods:
- Utilized the relativistic coupled-cluster method with single, double, and perturbative triple excitations (CCSD(T)).
- Incorporated scalar-relativistic, spin-orbit coupling (SOC), and fully relativistic Dirac-Coulomb Hamiltonians.
- Evaluated the influence of electron correlation across different relativistic regimes.
Main Results:
- Obtained recommended static dipole polarizabilities: Cu (46.91 ± 1.31 a.u.), Ag (50.97 ± 1.93 a.u.), and Au (36.68 ± 0.78 a.u.).
- Results show excellent agreement with previous recommendations, featuring reduced uncertainties for Ag and Au.
- Scalar-relativistic effects were found to be the dominant relativistic contribution, while SOC effects were negligible.
Conclusions:
- The relativistic coupled-cluster method provides accurate static dipole polarizabilities for group 11 elements.
- Scalar-relativistic effects significantly influence polarizabilities, whereas spin-orbit coupling effects are minimal for these elements.
- Electron correlation plays a vital role in achieving precise polarizability calculations across all relativistic frameworks.
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