Distance-including rigorous upper bounds and tight estimates for two-electron integrals over long- and short-range operators

The Journal of Chemical Physics, 147, 144101 (2017); https://doi.org/10.1063/1.4994190
The Journal of Chemical Physics, online article

We introduce both rigorous and non-rigorous distance-dependent integral estimates for four-center two-electron integrals derived from a distance-including Schwarz-type inequality. The estimates are even easier to implement than our so far most efficient distance-dependent estimates [S. A. Maurer et al., J. Chem. Phys. 136, 144107 (2012)] and, in addition, do not require well-separated charge-distributions. They are also applicable to a wide range of two-electron operators such as those found in explicitly correlated theories and in short-range hybrid density functionals. For two such operators with exponential distance decay [er12 and erfc(0.11⋅r12)/r12], the rigorous bound is shown to be much tighter than the standard Schwarz estimate with virtually no error penalty. The non-rigorous estimate gives results very close to an exact screening for these operators and for the long-range 1/r12 operator, with errors that are completely controllable through the integral screening threshold. In addition, we present an alternative form of our non-rigorous bound that is particularly well-suited for improving the PreLinK method [J. Kussmann and C. Ochsenfeld, J. Chem. Phys. 138, 134114 (2013)] in the context of short-range exchange calculations.

TU München
Helmholtz München
MPI of Neurobiology
MPI of Biochemistry