32.9 Doing it right

The local correlation methods in MOLPRO employ localized molecular orbitals (LMOs). Pipek-Mezey localization is recommended, but Boys localization is also possible. The virtual orbital space is spanned by non-orthogonal projected atomic orbitals (PAOs). The local character of this basis makes it possible to introduce two distinct approximations: first, excitations are restricted to domains, which are subspaces of (PAOs) that are spatially close to the orbitals from which the electrons are being excited. Secondly, the orbital pairs are classified according to their importance (based on distance or connectivity criteria), and only strong pairs are treated at the highest level (e.g. CCSD). The remaining weak and distant pairs are treated at the LMP2 level, and very distant pairs are neglected. These approximations lead to linear scaling of the computational resources as a function of the molecular size.

Naturally, such approximation can introduce some errors, and therefore the user has to be more careful than with standard black box methods. On the other hand, the low-order scaling makes it possible to treat much larger systems at high levels of theory than it was possible so far.

This section summarizes some important points to remember when performing local correlation calculations.

molpro@molpro.net 2019-06-18