English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

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

MPS-Authors
/persons/resource/persons237583

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

/persons/resource/persons216825

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

External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
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: https://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.