Prediction of the inner-shell contribution to the correlation energy through DLPNO-CEPA/1 and Scaled same-spin second order M{\o}ller-Plesset perturbation theory

TL;DR

This paper evaluates low-cost computational methods, SSS-MP2 and DLPNO-CEPA/1, for accurately predicting the inner-shell contribution to correlation energy, demonstrating significant improvements over traditional approaches.

Contribution

It introduces a reparameterized SSS-MP2 method and combines it with DLPNO-CEPA/1 to enhance prediction accuracy of inner-shell correlation energies.

Findings

SSS-MP2 reduces RMSE from 0.443 to 0.302 kcal/mol.

DLPNO-CEPA/1 achieves an RMSE of 0.147 kcal/mol.

Combining both methods further decreases RMSE to 0.118 kcal/mol.

Abstract

The use of two low cost methods for the prediction of the inner-shells contribution to the correlation energy is analyzed. The Spin-Component-Scaled second order M{\o}ller-Plesset perturbation theory (SCS-MP2) was reparameterized for the prediction of such contributions. The best results are found when only the same spin term is considered (SSS-MP2). The Coupled Electron Pair Approximation (CEPA) using the domain based local pair natural orbital approximation (DLPNO) was also studied for the same purpose. The methods were tested on the W4-11 test set using basis sets up to quadruple zeta quality. The SSS-MP2 proved to be a marked improvement upon MP2 decreasing the root-mean-square-error (RMSE) from 0.443 to 0.302 kcal/mol. The RMSE of DLPNO-CEPA/1 in the test set is only 0.147 kcal/mol and its computational cost is very low considering the intended applications. Furthermore, a linear combination of both methods decreased the RMSE to 0.118 kcal/mol.