화학공학소재연구정보센터
Journal of Chemical Physics, Vol.116, No.23, 10122-10128, 2002
A highly efficient algorithm for electron repulsion integrals over relativistic four-component Gaussian-type spinors
In the previous studies, a highly efficient computational scheme has been proposed for the Dirac-Hartree-Fock and the Dirac-Kohn-Sham solutions using the generally contracted kinetically balanced Gaussian-type spinors (GTSs). Nevertheless, the calculations based on the full Dirac Hamiltonian are limited to small systems if they contain heavy elements. The bottleneck is the calculation of the two-electron repulsions over the four-component GTSs. The present paper presents an improved algorithm for evaluation of the four-component relativistic integrals. The new algorithm fully exploits the transfer relation of Head-Gordon and Pople (HGP) and the accompanying coordinate expansion (ACE) formulas of Ishida. The HGP transfer relation can reduce the four-component integrals into several common two-center integrals (p0parallel toq0), which can be computed rapidly using the ACE method. The algorithm is implemented into the four-component program system REL4D. Benchmark calculations demonstrate that a good performance is achieved, particularly for the calculation of the (SS\SS) integrals.