Assessment of DLPNO-MP2 Approximations in Double-Hybrid DFT

16 August 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The unfavorable scaling (N5) of conventional second-order Møller-Plesset theory (MP2) typically prevents the application of double-hybrid (DH) density functionals to large systems with more than 100 atoms. A prominent approach to reduce the computational demand of electron correlation methods is the domain-based local pair natural orbital (DLPNO) approximation that is successfully used in the framework of DLPNO-CCSD(T). Its extension to MP2 [P. Pinski, C. Riplinger, E. F. Valeev and F. Neese, J. Chem. Phys. 143, 034108 (2015)] paved the way for DLPNO-MP2-based double-hybrid methods. In this work, we assess the accuracy of the DLPNO-MP2 approximation compared to conventional double-hybrids on a large number of 7925 data points for thermochemistry and 239 data points for structural features, including main-group and transition-metal systems. It is shown that DLPNO-DH-DFT can be applied successfully to perform energy calculations and geometry optimizations for large molecules at a drastically reduced computational cost. Furthermore, PNO space extrapolation is shown to be applicable, similar to its DLPNO-CCSD(T) counterpart, to reduce the remaining error.



Supplementary materials

Supporting Information
Statistical measures and supplementary data


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