We propose to construct electron correlation methods that are scalable in both molecule size and aggregated parallel computational power, in the sense that the total elapsed time of a calculation becomes nearly independent of the molecular size when the number of processors grows linearly with the molecular size. This is shown to be possible by exploiting a combination of local approximations and parallel algorithms. The concept is demonstrated with a linear scaling pair natural orbital local second-order Møller-Plesset perturbation theory (PNO-LMP2) method. In this method, both the wave function manifold and the integrals are transformed incrementally from projected atomic orbitals (PAOs) first to orbital-specific virtuals (OSVs) and finally to pair natural orbitals (PNOs), which allow for minimum domain sizes and fine-grained accuracy control using very few parameters. A parallel algorithm design is discussed, which is efficient for both small and large molecules, and numbers of processors, although true inverse-linear scaling with compute power is not yet reached in all cases. Initial applications to reactions involving large molecules reveal surprisingly large effects of dispersion energy contributions as well as large intramolecular basis set superposition errors in canonical MP2 calculations. In order to account for the dispersion effects, the usual selection of PNOs on the basis of natural occupation numbers turns out to be insufficient, and a new energy-based criterion is proposed. If explicitly correlated (F12) terms are included, fast convergence to the MP2 complete basis set (CBS) limit is achieved. For the studied reactions, the PNO-LMP2-F12 results deviate from the canonical MP2/CBS and MP2-F12 values by <1 kJ mol(-1), using triple-ζ (VTZ-F12) basis sets.

Explicitly correlated local coupled-cluster (LCCSD-F12) methods with pair natural orbitals (PNOs), orbital specific virtual orbitals (OSVs), and projected atomic orbitals (PAOs) are compared. In all cases pair-specific virtual subspaces (domains) are used, and the convergence of the correlation energy as a function of the domain sizes is studied. Furthermore, the performance of the methods for reaction energies of 52 reactions involving 58 small and medium sized molecules is investigated. It is demonstrated that for all choices of virtual orbitals much smaller domains are needed in the explicitly correlated methods than without the explicitly correlated terms, since the latter correct a large part of the domain error, as found previously. For PNO-LCCSD-F12 with VTZ-F12 basis sets on the average only 20 PNOs per pair are needed to obtain reaction energies with a root mean square deviation of less than 1 kJ mol(-1) from complete basis set estimates. With OSVs or PAOs at least 4 times larger domains are needed for the same accuracy. A new hybrid method that combines the advantages of the OSV and PNO methods is proposed and tested. While in the current work the different local methods are only simulated using a conventional CCSD program, the implications for low-order scaling local implementations of the various methods are discussed.

We present a (near) linear scaling implementation of high-spin open-shell Møller–Plesset perturbation theory using pair natural orbitals (PNO-RMP2). The theory is based on a new variant of open-shell MP2 which is fully spin-adapted and uses a single set of spin-free amplitudes, as in closed-shell MP2. This method, denoted SROMP2, is invariant to unitary orbital transformations within the closed, open, and virtual orbital subspaces. Accordingly, only a single set of PNOs per spatial orbital pair is needed, and the efficiency is similar to closed-shell calculations. The PNOs are obtained using a semicanonical approximation with large domains of projected atomic orbitals (PAOs). Linear scaling is achieved provided that the open-shell orbitals are local, and distant pairs are treated by multipole approximations. The method is efficiently parallelized. The convergence of ionization and reaction energies as a function of the PAO and PNO domain sizes is demonstrated and found to be very similar as for closed-shell calculations. The suitability of the PNOs for explicitly correlated PNO-RCCSD-F12 calculations is also tested. So far, this method is only simulated using a conventional program with appropriate projections to the PAO and PNO subspaces. It is demonstrated for radical stabilization energies as well as ionization potentials that the errors caused by the local domain approximations with our default thresholds are negligible.

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