Can Popular DFT Approximations and Truncated Coupled Cluster Theory Describe the Potential Energy Surface of the Beryllium Dimer?

Title
Can Popular DFT Approximations and Truncated Coupled Cluster Theory Describe the Potential Energy Surface of the Beryllium Dimer?
Publication Date
2018
Author(s)
Karton, Amir
( author )
OrcID: https://orcid.org/0000-0002-7981-508X
Email: akarton@une.edu.au
UNE Id une-id:akarton
McKemmish, Laura K
Type of document
Journal Article
Language
en
Entity Type
Publication
Publisher
CSIRO Publishing
Place of publication
Australia
DOI
10.1071/CH18269
UNE publication id
une:1959.11/51319
Abstract

The potential energy surface (PES) of the ground state of the beryllium dimer poses a significant challenge for high-level ab initio electronic structure methods. Here, we present a systematic study of basis set effects over the entire PES of Be2 calculated at the full configuration interaction (FCI) level. The reference PES is calculated at the valence FCI/cc-pV{5,6}Z level of theory. We find that the FCI/cc-pV{T,Q}Z basis set extrapolation reproduces the shape of the FCI/cc-pV{5,6}Z PES as well as the binding energy and vibrational transition frequencies to within ~10 cm-1. We also use the FCI/cc-pV{5,6}Z PES to evaluate the performance of truncated coupled cluster methods (CCSD, CCSD(T), CCSDT, and CCSDT(Q)) and contemporary density functional theory methods (DFT) methods for the entire PES of Be2. Of the truncated coupled cluster methods, CCSDT(Q)/cc-pV{5,6}Z provides a good representation of the FCI/cc-pV{5,6}Z PES. The GGA functionals, as well as the HGGA and HMGGA functionals with low percentages of exact exchange tend to severely overbind the Be2 dimer, whereas BH&HLYP and M06-HF tend to underbind it. Range-separated DFT functionals tend to underbind the dimer. Double-hybrid DFT functionals show surprisingly good performance, with DSD-PBEP86 being the best performer. Møller-Plesset perturbation theory converges smoothly up to fourth order; however, fifth-order corrections have practically no effect on the PES.

Link
Citation
Australian Journal of Chemistry, 71(10), p. 804-810
ISSN
1445-0038
0004-9425
Start page
804
End page
810

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