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

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.

journal_name

Photosynth Res

journal_title

Photosynthesis research

authors

Nottoli M,Jurinovich S,Cupellini L,Gardiner AT,Cogdell R,Mennucci B

doi

10.1007/s11120-018-0492-1

subject

Has Abstract

pub_date

2018-08-01 00:00:00

pages

215-226

issue

2

eissn

0166-8595

issn

1573-5079

pii

10.1007/s11120-018-0492-1

journal_volume

137

pub_type

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