We introduce a method for obtaining atomic point-charges that yield accurate representations of the electrostatic potentials (ESP) of large systems. The method relies on a decomposition of the density and subsequent projection of the multipole moments of the density components onto neighbouring atomic sites. The resulting local multipole-derived charges (LMDCs) are well-defined, do not require sampling of the ESP at grid points around the molecule and provide a good description of the

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... tic potential. This local approach circumvents the numerical problems that arose in our original method which was designed to find the optimal atomic charge representation of the ESP of a system outside the electron density.