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Accurate thermochemistry from a parameterized coupled-cluster singles and doubles model and a local pair natural orbital based implementation for applications to larger systems

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Hansen,  Andreas
Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Citation

Huntington, L. M. J., Hansen, A., Neese, F., & Nooijen, M. (2012). Accurate thermochemistry from a parameterized coupled-cluster singles and doubles model and a local pair natural orbital based implementation for applications to larger systems. The Journal of Chemical Physics, 136(6): 064101. doi:10.1063/1.3682325.


Cite as: http://hdl.handle.net/21.11116/0000-0007-E5A3-E
Abstract
We have recently introduced a parameterized coupled-cluster singles and doubles model (pCCSD(α, β)) that consists of a bivariate parameterization of the CCSD equations and is inspired by the coupled electron pair approximations. In our previous work, it was demonstrated that the pCCSD(−1, 1) method is an improvement over CCSD for the calculation of geometries, harmonic frequencies, and potential energy surfaces for single bond-breaking. In this paper, we find suitable pCCSD parameters for applications in reaction thermochemistry and thermochemical kinetics. The motivation is to develop an accurate and economical methodology that, when coupled with a robust local correlation framework based on localized pair natural orbitals, is suitable for large-scale thermochemical applications for sizeable molecular systems. It is demonstrated that the original pCCSD(−1, 1) method and several other pCCSD methods are a significant improvement upon the standard CCSD approach and that these methods often approach the accuracy of CCSD(T) for the calculation of reaction energies and barrier heights. We also show that a local version of the pCCSD methodology, implemented within the local pair natural orbital (LPNO) based CCSD code in ORCA, is sufficiently accurate for wide-scale chemical applications. The LPNO based methodology allows us for routine applications to intermediate sized (20–100 atoms) molecular systems and is a significantly more accurate alternative to MP2 and density functional theory for the prediction of reaction energies and barrier heights.