Work

Organodichalcogenide Structure and Stability: Hierarchical Ab Initio Benchmark and DFT Performance Study

Year: 2025

Type: article

Abstract: ABSTRACT We conducted a double‐hierarchical ab initio benchmark and DFT performance study of the organodichalcogenide bonding motif CH3Ch1Ch2(O)nCH3 with Ch1, Ch2 = S, Se and n = 0, 1, 2. The organodichalcogenide model systems were optimized at ZORA‐CCSD(T)/ma‐ZORA‐def2‐TZVPP. Our ab initio benchmark involved a hierarchical series of all‐electron relativistically contracted variants of the Karlsruhe basis sets (ZORA‐def2‐SVP, ZORA‐def2‐TZVPP, ZORA‐def2‐QZVPP), both with and without diffuse functions (ma‐basis set), in conjunction with a hierarchical series of ZORA‐relativistic quantum chemical methods [HF, MP2, CCSD, and CCSD(T)]. Counterpoise correction was applied to account for the basis set superposition error (BSSE). We assessed the performance of 33 ZORA‐relativistic DFT functionals (ZORA‐[XC functional]/TZ2P//ZORA‐[XC functional]/TZ2P) against our benchmark energies and found that M06 and MN15 furnish accurate geometries and bond energies within a mean absolute error of 1.2 kcal mol−1 relative to our best ab initio reference data.

Source: Journal of Computational Chemistry

DOI: 10.1002/jcc.70142

Authors: Steven E. Beutick, Francesco Lambertini, Trevor A. Hamlin, F. Matthias Bickelhaupt, Laura Orian

Institutions: University of Padua, Vrije Universiteit Amsterdam, Radboud University Nijmegen, University of Johannesburg

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,520

Funders: Fondazione Cassa di Risparmio di Padova e Rovigo, Nederlandse Organisatie voor Wetenschappelijk Onderzoek, Università degli Studi di Padova