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...

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Bibliographic Details
Published in:Journal of Chemical Theory and Computation
Main Authors: Demel, O. (Ondřej), Pittner, J. (Jiří), Neese, F.
Format: Article in Journal/Newspaper
Language:English
Published: 2015
Subjects:
ELECTRON CORRELATION METHODS
BRILLOUIN-WIGNER
CONFIGURATION-INTERACTION
Orca
Online Access:https://doi.org/10.1021/acs.jctc.5b00334
http://hdl.handle.net/11104/0247818
Description
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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