Communication: Multipole approximations of distant pair energies in local correlation methods with pair natural orbitals

The accuracy of multipole approximations for distant pair energies in local second-order Moller-Plesset perturbation theory (LMP2) as introduced by Hetzer et al. [Chem. Phys. Lett. 290, 143 (1998)] is investigated for three chemical reactions involving molecules with up to 92 atoms. Various iterative and non-iterative approaches are compared, using different energy thresholds for distant pair selection. It is demonstrated that the simple non-iterative dipole-dipole approximation, which has been used in several recent pair natural orbitals (PNO)-LMP2 and PNO-LCCSD (local coupled-cluster with singles and doubles) methods, may underestimate the distant pair energies by up to 50% and can lead to significant errors in relative energies, unless very tight thresholds are used. The accuracy can be much improved by including higher multipole orders and by optimizing the distant pair amplitudes iteratively along with all other amplitudes. A new approach is presented in which very small special PNO domains for distant pairs are used in the iterative approach. This reduces the number of distant pair amplitudes by 3 orders of magnitude and keeps the additional computational effort for the iterative optimization of distant pair amplitudes minimal. Published by AIP Publishing.