Benchmark study of DFT and composite methods for bond dissociation energies in argon compounds

Abstract

We introduce a database of 14 accurate bond dissociation energies (BDEs) of noble gas compounds. Reference CCSD(T)/CBS BDEs are obtained by means of W1 theory. We evaluate the performance of contemporary density functional theory (DFT), double-hybrid DFT (DHDFT), and composite ab initio procedures. A general improvement in performance is observed along the rungs of Jacob’s Ladder; however, only a handful of functionals give good performance for predicting the bond dissociation energies in the NGC14 database. Thus, this database represents a challenging test for DFT methods. Most of the conventional DFT functionals (71%) result in root-mean-square deviations (RMSDs) between 10.0 and 82.1 kJ mol−1. The rest of the DFT functionals attain RMSDs between 2.5 and 8.9 kJ mol−1. The best performing functionals from each rung of Jacob’s Ladder are (RMSD given in parenthesis): HCTH407 (30.9); M06-L (5.4); PBE0 (2.8); B1B95, M06, and PW6B95 (2.7–2.9); CAM-B3LYP-D3 (5.4); and B2T-PLYP (2.5 kJ mol−1).