A Local Pair Natural Orbital-Based Multireference Mukherjee’s Coupled Cluster Method
This paper reports the development of a local variant of Mukherjee’s state-specific multireference coupled cluster method based on the pair natural orbital approach (LPNO-MkCC). The current implementation is restricted to single and double excitations. The performance of the LPNO-MkCCSD method was t...
Published in: | Journal of Chemical Theory and Computation |
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Main Authors: | , , |
Format: | Article in Journal/Newspaper |
Language: | English |
Published: |
2015
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Subjects: | |
Online Access: | https://doi.org/10.1021/acs.jctc.5b00334 http://hdl.handle.net/11104/0247818 |
Summary: | This paper reports the development of a local variant of Mukherjee’s state-specific multireference coupled cluster method based on the pair natural orbital approach (LPNO-MkCC). The current implementation is restricted to single and double excitations. The performance of the LPNO-MkCCSD method was tested on calculations of naphthyne isomers, tetramethyleneethane, and β-carotene molecules. The results show that 99.7–99.8% of correlation energy was recovered with respect to the MkCC method based on canonical orbitals. Moreover, the errors of relative energies between different isomers or along a potential energy curve (with respect to the canonical method) are below 0.4 kcal/mol, safely within the chemical accuracy. The computational efficiency of our implementation of LPNO-MkCCSD in the ORCA program allows calculation of the β-carotene molecule (96 atoms and 1984 basis functions) on a single CPU core. |
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