Considering calculations of the molecular electrostatic potential at the atomic sites (MEP@AS) in the presence of effective core potentials (ECP), we found that the consequent use of the definition of MEP@AS based on the energy derivative with respect to nuclear charge leads to a formula that differs by one term from the result of simple application of Coulomb's law. We have developed a general method to analytically treat derivatives of ECP with respect to nuclear charge. Benchmarking calculations performed on a set of simple molecules show that our formula leads to a systematic decrease in the error connected with the introduction of ECP when compared to all-electron results. Because of a straightforward implementation and relatively low costs of the developed procedure we suggest to use it by default.
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Research Article| February 19 2013
Molecular electrostatic potential at the atomic sites in the effective core potential approximation
Michał Lesiuk, Janusz Zachara; Molecular electrostatic potential at the atomic sites in the effective core potential approximation. J. Chem. Phys. 21 February 2013; 138 (7): 074107. https://doi.org/10.1063/1.4792198
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