A non-iterative density functional describing the core-valence correlation energy (CV-DFT) was applied to 113 species for the first- and second-row of the periodic table including alkaline and alkaline earth metals and ions. Compared to CCSD(T)/MTsmall, CV-DFT/3Za1Pa gave 1.28 kJ mol-1 RMS error for 87 chemical reactions and ionizations, whereas MP2/MTsmall gave 1.55 kJ mol-1 RMS error. The valence CCSD(T) error relative to FCI is 2.52 kJ mol-1. The CV-DFT procedure significantly reduces the cost of high-accuracy thermochemical calculations. 

Density functional for core-valence correlation energy

248th National Meeting (2014)

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