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Molecular QTAIM Topology Is Sensitive to Relativistic Corrections |
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| Authors: | Prof. James S. M. Anderson Prof. Juan I. Rodríguez Prof. Paul W. Ayers Daniel E. Trujillo-González Dr. Andreas W. Götz Prof. Jochen Autschbach Prof. Fray L. Castillo-Alvarado Prof. Koichi Yamashita |
| Affiliation: | 1. Department of Chemistry & Chemical Biology, McMaster University, Hamilton, Ontario, L8S4M1 Canada;2. Escuela Superior de Física y Matemáticas, Instituto Politécnico Nacional, Edificio 9, U.P. A.L.M, Col. San Pedro Zacatenco, C.P., 07738 Ciudad de México, México;3. San Diego Supercomputer Center, University of California San Diego, 9500 Gilman Drive, La Jolla, 92093-0505 California, USA;4. Department of Chemistry, University at Buffalo, State University of New York, Buffalo, 14260-3000 NY, USA;5. Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656 Japan |
| Abstract: | The topology of the molecular electron density of benzene dithiol gold cluster complex Au4−S−C6H4−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. |
| Keywords: | Amsterdam density functional computational chemistry quantum theory of atoms in molecules topology |