How Can The Relativistic Effects On The 6s Orbital Of Gold In Aurophilic Interactions Be Accurately Quantified Using Density Functional Theory, And What Implications Might This Have For The Design Of New Gold-based Supramolecular Complexes With Enhanced Pi-backbonding Capabilities?

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To accurately quantify relativistic effects on the 6s orbital of gold in aurophilic interactions using density functional theory (DFT) and to explore implications for designing new gold-based supramolecular complexes with enhanced pi-backbonding, the following approach is proposed:

Quantifying Relativistic Effects in DFT

  1. Incorporate Relativistic Corrections: Utilize DFT methods that include relativistic effects, such as scalar relativistic corrections. These can be implemented through approaches like the zeroth-order regular approximation (ZORA), which effectively accounts for relativistic effects without the computational complexity of full relativistic methods.

  2. Use Appropriate Functionals and Basis Sets: Select DFT functionals and basis sets designed for heavy elements. These should account for the relativistic contraction and stabilization of the 6s orbital, ensuring accurate modeling of gold's electronic structure.

  3. Consider Spin-Orbit Coupling: While scalar relativistic effects are crucial, spin-orbit coupling, particularly significant for heavier elements, should also be considered to understand fully the splitting of d orbitals and their impact on backbonding.

Implications for Designing Gold-Based Complexes

  1. Enhanced Pi-Backbonding: Relativistic effects stabilize and contract the 6s orbital, potentially enhancing its role in pi-backbonding. This can be leveraged by selecting ligands with suitable acceptor orbitals and geometries that optimize these interactions.

  2. Optimized Supramolecular Structures: Design complexes where the arrangement of gold centers maximizes aurophilic interactions, informed by accurate DFT models that account for relativistic effects on the 6s orbital.

  3. Potential Applications: Improved pi-backbonding could lead to materials with enhanced catalytic activity or unique optical properties, as electronic transitions in such complexes are influenced by backbonding strength.

Conclusion

By integrating relativistic corrections into DFT, researchers can better understand the role of the 6s orbital in aurophilic interactions and pi-backbonding. This understanding can guide the design of new gold-based complexes with tailored electronic properties, potentially advancing their applications in catalysis and materials science.