Nuclear cusp conditions and their fulfillment in molecular calculations with SLATER basis sets



A short revision of the main antecedents on the nuclear cusp conditions is followed by a derivation of the general expressions of the conditions which must be accomplished by wave functions and densities. It is stressed that in case of the molecular densities, besides Kato's cusp condition, there are also simple cusp conditions for the three dipole-type terms of the densities but not for terms of order higher than dipole. The degree of fulfillment of standard atomic and molecular calculations with Slater basis sets is tested, concluding that errors of spherical terms usually affect the third or fourth significant figures, being smaller as nuclear charges increase, and the errors of dipole-type components are greater than those of the spherical terms. In practice, improvements in the computational method or in the basis set do not guarantee a better fulfillment of the cusp conditions. Hydrogen is a special case which can yield poor results. © 2014 Wiley Periodicals, Inc.