Reproducing benchmark potential energy curves of molecular bond dissociation with small complete active space aided...

Various effects of electron correlation accompany molecular bond dissociation, which makes the efficient calculation of potential energy curves a notoriously difficult problem. In an attempt to reliably reproduce both absolute energies and shapes of the benchmark dissociation curves, calculations with the combined CASΠDFT method are carried out for the prototype molecules H₂, BH, F₂, and N₂. The complete active space (CAS) part of CASΠDFT accounts for long-range nondynamic correlation, while short-range dynamic correlation is accounted for with the corrected Lee-Yang-Parr correlation functional of density functional theory (DFT). The correction represents the suppression of dynamic correlation with nondynamic correlation, and it is a function of the ratio x(r) between the conditional and conventional densities obtained with the CAS on-top pair density Π(r). For the single-bonded molecules H₂, BH, and F₂, CASΠDFT succeeds in reproducing the shapes and absolute energies (for H₂ and BH) of the benchmark curves, while for the triple-bonded N₂ molecule, the addition to CASΠDFT of a multibond correction is required. It accounts for the middle-range dynamic correlation of the same-spin electrons in the (symmetrized) high-spin atomic electron configurations of the dissociating N₂.