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Journal of Chemical Physics / Volume 132 / Issue 15 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 132, 154103 (2010); doi:10.1063/1.3385315 (11 pages)

Active-space completely-renormalized equation-of-motion coupled-cluster formalism: Excited-state studies of green fluorescent protein, free-base porphyrin, and oligoporphyrin dimer

Karol Kowalski1, Sriram Krishnamoorthy2, Oreste Villa2, Jeff R. Hammond3, and Niranjan Govind1

1William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA
2Computational Sciences and Mathematics Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA
3Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439, USA

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(Received 7 October 2009; accepted 18 March 2010; published online 16 April 2010)

The completely renormalized equation-of-motion coupled-cluster approach with singles, doubles, and noniterative triples [CR-EOMCCSD(T)] has proven to be a reliable tool in describing vertical excitation energies in small and medium size molecules. In order to reduce the high numerical cost of the genuine CR-EOMCCSD(T) method and make noniterative CR-EOMCCSD(T) approaches applicable to large molecular systems, two active-space variants of this formalism [the CR-EOMCCSd(t)-II and CR-EOMCCSd(t)-III methods], based on two different choices of the subspace of triply excited configurations employed to construct noniterative correction, are introduced. In calculations for green fluorescent protein (GFP) and free-base porphyrin, where the CR-EOMCCSD(T) results are available, we show good agreement between the active-space CR-EOMCCSD(T) (variant II) and full CR-EOMCCSD(T) excitation energies. For the oligoporphyrin dimer (P2TA) active-space CR-EOMCCSD(T) results provide reasonable agreement with experimentally inferred data. For all systems considered we demonstrated that the active-space CR-EOMCCSD(T) corrections lower the EOMCCSD (iterative equation-of-motion coupled-cluster method with singles and doubles) excitation energies by 0.2 and 0.3 eV, which leads to a better agreement with experiment. We also discuss the quality of basis sets used and compare EOMCC excitation energies with excitation energies obtained with other methods. In particular, we demonstrate that for GFP and FBP Sadlej’s TZP and cc-pVTZ basis sets lead to a similar quality of the EOMCC results. The performance of the CR-EOMCCSD(T) implementation is discussed from the point of view of timings of iterative parts and scalability of the most expensive, N7, part of the calculation. In the latter case the scalability across 34 008 processors is reported.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. THEORY
  3. RESULTS AND DISCUSSION
    1. Basis sets and system specifications
    2. Computational and performance details
    3. GFP chromophore
    4. Free base porphyrin
    5. P2TA
  4. CONCLUSIONS

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KEYWORDS and PACS

Keywords

coupled cluster calculations, excited states, iterative methods, molecular biophysics, proteins

PACS

ARTICLE DATA

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http://link.aip.org/link/doi/10.1063/1.3385315

PUBLICATION DATA

ISSN:

0021-9606 (print)  
1089-7690 (online)

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$abstract.society.value is a Member of CrossRef American Institute of Physics

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