Prediction of the inner-shell contribution to the correlation energy through DLPNO-CEPA/1 and Scaled same-spin second order Møller-Plesset perturbation theory

Fuente: arXiv
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Main Author: Sánchez, Hernán R.
Format: Preprint
Published: 2019
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author Sánchez, Hernán R.
author_facet Sánchez, Hernán R.
contents 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 Møller-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.
format Preprint
id arxiv_https___arxiv_org_abs_1911_11764
institution arXiv
publishDate 2019
record_format arxiv
spellingShingle Prediction of the inner-shell contribution to the correlation energy through DLPNO-CEPA/1 and Scaled same-spin second order Møller-Plesset perturbation theory
Sánchez, Hernán R.
Chemical Physics
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 Møller-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.
title Prediction of the inner-shell contribution to the correlation energy through DLPNO-CEPA/1 and Scaled same-spin second order Møller-Plesset perturbation theory
topic Chemical Physics
url https://arxiv.org/abs/1911.11764