Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Abstract

The “Swiss army knife” composite density functional electronic-structure method r 2 SCAN-3c ( J. Chem. Phys. 2021 , 154 , 064103) is extended and optimized for the use with Slater-type orbital basis sets. The meta generalized-gradient approximation (meta-GGA) functional r 2 SCAN by Furness et al. is combined with a tailor-made polarized triple-ζ Slater-type atomic orbital (STO) basis set (mTZ2P), the semiclassical London dispersion correction (D4), and a geometrical counterpoise (gCP) correction. Relativistic effects are treated explicitly with the scalar-relativistic zeroth-order regular approximation (SR-ZORA). The performance of the new implementation is assessed on eight geometry and 74 energy benchmark sets, including the extensive GMTKN55 database as well as recent sets such as ROST61 and IONPI19. In geometry optimizations, the STO-based r 2 SCAN-3c is either on par with or more accurate than the hybrid density functional approximation M06-2X-D3(0)/TZP. In energy calculations, the overall accuracy is similar to the original implementation of r 2 SCAN-3c with Gaussian-type atomic orbitals (GTO), but basic properties, intermolecular noncovalent interactions, and barrier heights are better described with the STO approach, resulting in a lower weighted mean absolute deviation (WTMAD-2(STO) = 7.15 vs 7.50 kcal mol –1 with the original method) for the GMTKN55 database. The STO-optimized r 2 SCAN-3c outperforms many conventional hybrid/QZ approaches in most common applications at a fraction of their cost. The reliable, robust, and accurate r 2 SCAN-3c implementation with STOs is a promising alternative to the original implementation with GTOs and can be generally used for a broad field of quantum chemical problems.

Synthesis and structural characterization of stable coinage metal (Cu, Ag, Au) cyclopentadienyl complexes

“…To further understand the trends in bonding between the [C 5 (CF 3 ) 5 ] − ligand and the coinage metals, scalar-relativistic ZORA-r 2 SCAN-3c 54 DFT calculations have been carried out. To allow for a simpler analysis, we replaced the t Bu groups of the phosphine ligand by methyl groups.…”

Understanding the Influence of Functional Groups on the PEO Composite Electrolytes through a Theoretical, Spectroscopic, and Conduction Behavior Study of Model Systems

“…In each round of energy sorting, duplicate structures were removed to ensure that the structures entering the next round contain a greater diversity of conformations. After the first round of optimization using the GFN2-xTB method, the single-point energy was calculated using the r 2 SCAN-3c , method of ORCA 5.0, and the first 20 frames of the structure were selected for the second round of screening. In the second round of screening, the geometries were optimized by using Gaussian software at B3LYP-D3 , /def2-SVP level; the SMD solvent model with tetrahydrofuran (THF) solvent was used to consider the solvation effect.…”

Benchmark Study on the Calculation of 207Pb NMR Chemical Shifts

“…To investigate the influence of the applied method in the geometry optimization, the lowest-lying conformer of each ensemble was reoptimized with the SQM methods GFN1- and GFN2-xTB, the GFN-FF force field, as well as with the SR- and SO-ZORA variants of r 2 SCAN-3c(STO), 84 as implemented in ADF. Solvation effects were treated with the ALPB and COSMO solvation models, respectively.…”