GDB9-W1-F12 database of CCSD(T)/CBS total atomization energies for 3366 organic species from W1-F12 theory.

The total atomization energy (TAE) is the most challenging thermochemical property for benchmarking density functional theory (DFT). We obtain the TAEs of 3366 molecules consisting of up to eight non-hydrogen atoms from the GDB-9 database at the CCSD(T)/CBS level using the high-level W1-F12 theory. This represents the largest and most diverse database of TAEs with confident sub-chemical accuracy for organic molecules. This database is used to assess the performance of 30 DFT functionals. The best-performing method from each rung of Jacob’s Ladder is (mean-absolute-deviation in parentheses): pure-GGA B97-D (4.67), meta-GGA M06-L (4.56), hybrid-GGA B3LYP (3.56), and hybrid-meta-GGA t-HCTHh (6.88 kcal/mol).