Efficient linear-scaling second-order Møller-Plesset perturbation theory: The divide–expand–consolidate RI-MP2 model

• Published in: The Journal of chemical physics 2016-02, Vol.144 (5)
• Main Authors: Baudin, Pablo, Ettenhuber, Patrick, Reine, Simen, Kristensen, Kasper, Kjærgaard, Thomas
• Format: Article
• Language: English
• Subjects: Chemistry; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Physics
• ISSN: 0021-9606; 1089-7690

The Resolution of the Identity second-order Møller-Plesset perturbation theory (RI-MP2) method is implemented within the linear-scaling Divide-Expand-Consolidate (DEC) framework. In a DEC calculation, the full molecular correlated calculation is replaced by a set of independent fragment calculations each using a subset of the total orbital space. The number of independent fragment calculations scales linearly with the system size, rendering the method linear-scaling and massively parallel. The DEC-RI-MP2 method can be viewed as an approximation to the DEC-MP2 method where the RI approximation is utilized in each fragment calculation. The individual fragment calculations scale with the fifth power of the fragment size for both methods. However, the DEC-RI-MP2 method has a reduced prefactor compared to DEC-MP2 and is well-suited for implementation on massively parallel supercomputers, as demonstrated by test calculations on a set of medium-sized molecules. The DEC error control ensures that the standard RI-MP2 energy can be obtained to the predefined precision. The errors associated with the RI and DEC approximations are compared, and it is shown that the DEC-RI-MP2 method can be applied to systems far beyond the ones that can be treated with a conventional RI-MP2 implementation.