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Abstract
Density functional theory (DFT) has been extensively benchmarked for energetic properties; however, less attention has been given to equilibrium structures and the effect of using a certain DFT geometry on subsequent energetic properties. We evaluate the performance of 52 contemporary DFT methods for obtaining the structures of 122 species in the W411GEOM database. This dataset includes a total of 246 unique bonds: 117 H─X, 65 X─Y, 49 X═Y, and 15 X═Y bonds (where X and Y are first and secondrow atoms) and 133 key bond angles: 96 XYH, 22 XYZ, and 15 HXH angles. The reference geometries are optimized at the CCSD(T)/julccpV(n+d)Z level of theory (n = 5, 6). The performance of DFT is evaluated in conjunction with the Def2nZVPP (n = T, Q), ccpV(T+d)Z, and julccpV(T+d)Z basis sets. The rootmeansquare deviations (RMSDs) over the bond distances of the best performing functionals from each rung of Jacob's Ladder are 0.0086 (SOGGA11), 0.0088 (τHCTH), 0.0059 (B3LYP), 0.0054 (TPSSh), and 0.0032 (DSDPBEP86) Å. We evaluate the effect of the choice of the DFT geometry on subsequent molecular energies calculated with W1F12 theory. Geometries obtained with GGA and MGGA methods result in large RMSDs in the subsequent W1F12 energies; however, six hybrid GGA functionals (B3LYP, B3P86, mPW3PBE, B3PW91, mPW1LYP, and X3LYP) result in an excellent performance with RMSDs between 0.25 and 0.30 kJ mol^{−1} relative to the CCSD(T)/CBS reference geometries. The B2GPPLYP and mPW2PLYP DHDFT methods result in nearCCSD(T) accuracy with RMSDs of 0.11 and 0.10 kJ mol^{−1}, respectively.
Original language  English 

Pages (fromto)  15901601 
Number of pages  12 
Journal  Journal of Computational Chemistry 
Volume  42 
Issue number  22 
Early online date  13 Jun 2021 
DOIs  
Publication status  Published  15 Aug 2021 
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 1 Finished

Highlevel quantum chemistry: From theory to applications
ARC Australian Research Council
27/12/17 → 28/02/22
Project: Research