Premium
Assessment and development of DFT with the expanded CUAGAU ‐2 set of group‐11 cluster systems
Author(s) -
Chan Bun
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26453
Subject(s) - cluster (spacecraft) , density functional theory , group (periodic table) , set (abstract data type) , robustness (evolution) , coupled cluster , computer science , mathematics , chemistry , computational chemistry , physics , molecule , quantum mechanics , biochemistry , gene , programming language
In the present study, we have compiled the expanded CUAGAU‐2 set of group‐11 (Cu, Ag, Au) cluster systems. It contains species that we find to be more challenging for density functional theory (DFT) methods, which are not represented in the previous set. In the prosses, we have also devised the W1X‐G0 method for cost‐effective calculation of accurate reaction energies for such species; it is comparable to the W1X‐2 composite protocol but with a more sophisticated treatment for core correlation, which is necessary for the group‐11 cluster systems. Our assessment of DFT methods shows the MN15 method to be one of the most accurate for CUAGAU‐2. Nonetheless, the CUAGAU‐2 systems are more challenging for even some of the most advanced DFT methods when compared with main‐group and molecular transition‐metal systems. To facilitate rapid development of functionals with better accuracy and robustness, we have statistically downsized the 123‐point CUAGAU‐2 set to smaller sets with 11 (CUAGAU‐2s) and 41 (CUAGAU‐2m) points. In a brief case study, we have used CUAGAU‐2m and other small test sets to revise the SCAN0 method. The results suggest that reducing %HF in SCAN0 from 25% to 10% (yielding the SCANh method) would lead to an overall better performance, as well as a more uniform accuracy over different properties. This exercise demonstrates the utility of the CUAGAU‐2(s/m) and our previously compiled test sets for the exploration of density functionals.