Molecular QTAIM Topology Is Sensitive to Relativistic Corrections.

Abstract

The topology of the molecular electron density of benzene dithiol gold cluster complex Au4 -S-C6 H4 -S -Au 4 changed when relativistic corrections were made and the structure was close to a minimum of the Born-Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.