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Photosynthesis Research

, Volume 137, Issue 2, pp 215–226 | Cite as

The role of charge-transfer states in the spectral tuning of antenna complexes of purple bacteria

  • Michele Nottoli
  • Sandro Jurinovich
  • Lorenzo Cupellini
  • Alastair T. Gardiner
  • Richard Cogdell
  • Benedetta Mennucci
Original Article

Abstract

The LH2 antenna complexes of purple bacteria occur, depending on light conditions, in various different spectroscopic forms, with a similar structure but different absorption spectra. The differences are related to point changes in the primary amino acid sequence, but the molecular–level relationship between these changes and the resulting spectrum is still not well understood. We undertook a systematic quantum chemical analysis of all the main factors that contribute to the exciton structure, looking at how the environment modulates site energies and couplings in the B800–850 and B800–820 spectroscopic forms of LH2. A multiscale approach combining quantum chemistry and an atomistic classical embedding has been used where mutual polarization effects between the two parts are taken into account. We find that the loss of hydrogen bonds following amino acid changes can only explain a part of the observed blue-shift in the B850 band. The coupling of excitonic states to charge-transfer states, which is different in the two forms, contributes with a similar amount to the overall blue-shift.

Keywords

Excitonic model Antenna complex Quantum chemistry 

Notes

Acknowledgements

The authors are grateful to Dr. Aleksander W. Roszak for having provided the high-resolution X-ray structure of B800–850 complex. ATG and RJC gratefully acknowledge funding from the Photosynthetic Antenna Research Center, an Energy Frontier Research Center funded by the DOE, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC 0001035.

Supplementary material

11120_2018_492_MOESM1_ESM.pdf (901 kb)
Supplementary material 1 (PDF 901 KB)

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Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.Dipartimento di Chimica e Chimica IndustrialeUniversity of PisaPisaItaly
  2. 2.Glasgow Biomedical Research Centre, Institute of Molecular Cell and Systems BiologyUniversity of GlasgowGlasgowScotland, UK

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