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  Validation Challenge of Density-Functional Theory for Peptides—Example of Ac-Phe-Ala5-LysH+

Rossi, M., Chutia, S., Scheffler, M., & Blum, V. (2014). Validation Challenge of Density-Functional Theory for Peptides—Example of Ac-Phe-Ala5-LysH+. The Journal of Physical Chemistry A, 118(35), 7349-7359. doi:10.1021/jp412055r.

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 Creators:
Rossi, Mariana1, 2, Author           
Chutia, Sucismita1, Author           
Scheffler, Matthias1, Author           
Blum, Volker1, 3, Author           
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1Theory, Fritz Haber Institute, Max Planck Society, ou_634547              
2Physical and Theoretical Chemistry Laboratory, University of Oxford, OX1 3QZ Oxford, U.K., ou_persistent22              
3Department of Mechanical Engineering and Materials Science and Center for Materials Genomics, Duke University, Durham, North Carolina 27708, United States, ou_persistent22              

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 Abstract: We assess the performance of a group of exchange-correlation functionals for predicting the secondary structure of peptide chains, up to a new many-body dispersion corrected hybrid density functional, dubbed PBE0+MBD* by its original authors. For the purpose of validation, we first compare to published, high-level benchmark conformational energy hierarchies (coupled cluster at the singles, doubles, and perturbative triples level, CCSD(T)) for 73 conformers of small three-residue peptides, establishing that the van der Waals corrected PBE0 functional yields an average error of only ≈20 meV (≈0.5 kcal/mol). This compares to ≈40-50 meV for non-dispersion corrected PBE0 and 50-100 meV for different empirical force fields. For longer peptide chains that form secondary structure, CCSD(T) level benchmark data are currently unaffordable. We thus turn to the experimentally well studied Ac-Phe-Ala5-LysH+ peptide, for which four closely competing conformers were established by infrared spectroscopy. For comparison, an exhaustive theoretical conformational space exploration yields at least eleven competing low energy minima. We show that (i) the many-body dispersion correction, (ii) the hybrid functional nature of PBE0+MBD*, and (iii) zero-point corrections are needed to reveal the four experimentally observed structures as the minima that would be populated at low temperature.

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Language(s): eng - English
 Dates: 2014-01-082013-12-0920142014-01-092014-09-04
 Publication Status: Published in print
 Pages: 11
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jp412055r
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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 118 (35) Sequence Number: - Start / End Page: 7349 - 7359 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4