A new hierarchy of augmented basis sets optimized for the calculation of molecular properties such as indirect spin-spin coupling constants is presented. Based on the Dunning hierarchy of cc-pVXZ (X=D, T, Q, and 5) basis sets augmentation functions with tight exponents have been optimized for coupled-cluster calculations of indirect spin-spin coupling constants. The optimal exponents for these tight functions have been obtained by optimizing the sum of the absolute values of all contributions to the coupling constant. On the basis of a series of test cases (CO, HF, N-2, F-2, H2O, NH3, and CH4) we propose a set of tight s, p, and d functions to be added to the uncontracted Dunning basis sets, and, subsequently, to recontract. The resulting ccJ-pVXZ (X=D, T, Q, and 5) basis sets demonstrate excellent cost efficiency in benchmark calculations. These new basis sets should generally be applicable for the calculation of spin-spin coupling constants and other properties that have a strong dependence on powers of 1/r or even contain a delta distribution for correlated ab initio methods. (C) 2008 American Institute of Physics.