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Pushing the Limits of EOM-CCSD with Projector-Based Embedding for Excitation Energies

Bennie, Simon J.; Curchod, Basile F.E.; Manby, Frederick R.; Glowacki, David R.

Pushing the Limits of EOM-CCSD with Projector-Based Embedding for Excitation Energies Thumbnail


Authors

Simon J. Bennie

Frederick R. Manby

David R. Glowacki



Abstract

The calculation of accurate excitation energies using ab initio electronic structure methods such as standard equation of motion coupled cluster singles and doubles (EOM-CCSD) has been cost prohibitive for large systems. In this work, we use a simple projector-based embedding scheme to calculate the EOM-CCSD excitation energies of acrolein solvated in water molecules modeled using density functional theory (DFT). We demonstrate the accuracy of this approach gives excitation energies within 0.01 eV of full EOM-CCSD, but with significantly reduced computational cost. This approach is also shown to be relatively invariant to the choice of functional used in the environment and allows for the description of systems with large numbers of basis functions (>1000) to be treated using state-of-the-art wave function methods. The flexibility of embedding to select orbitals to add to the excited-state method provides insights into the origins of the excitations and can reduce artifacts that could arise in traditional linear response time-dependent DFT (LR-TDDFT).

Citation

Bennie, S. J., Curchod, B. F., Manby, F. R., & Glowacki, D. R. (2017). Pushing the Limits of EOM-CCSD with Projector-Based Embedding for Excitation Energies. Journal of Physical Chemistry Letters, 8(22), 5559-5565. https://doi.org/10.1021/acs.jpclett.7b02500

Journal Article Type Article
Acceptance Date Oct 27, 2017
Online Publication Date Oct 27, 2017
Publication Date Nov 16, 2017
Deposit Date Nov 6, 2017
Publicly Available Date Mar 29, 2024
Journal Journal of Physical Chemistry Letters
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 8
Issue 22
Pages 5559-5565
DOI https://doi.org/10.1021/acs.jpclett.7b02500

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Publisher Licence URL
http://creativecommons.org/licenses/by/4.0/

Copyright Statement
ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.




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