The effect of the electronic structure method and basis set on the accuracy of the electric multipoles computed with the distributed multipole analysis (DMA).

The molecular charge densities were computed using the electronic structure methods Hartree-Fock (HF), MP2, MP4, DFT/PBE, DFT/B3LYP, DFT/B3PW91, DFT/M06-2X, and DFT/B2PLYP implemented in the Gaussian 09 package. MP4 was the benchmark method. The DMA multipoles were obtained with the GDMA program of Stone. The 6-311G +  + (d,p) basis set was used for the production calculations, and the augmented correlation-consistent Dunning's hierarchy of basis sets was employed to evaluate the dependence of the DMA multipoles on the basis set size.