Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer

Zheng, Fulu; Fernandez-Alberti, Sebastian; Tretiak, Sergei; Zhao, Yang

doi:10.1021/acs.jpcb.7b02021

Title: Photoinduced Intra- and Intermolecular Energy Transfer in Chlorophyll a Dimer

Journal Article · Mon May 08 00:00:00 EDT 2017 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.7b02021· OSTI ID:1460648

Zheng, Fulu ^[1]; Fernandez-Alberti, Sebastian ^[2];

^[3];

^[1]

Nanyang Technological Univ. (Singapore). Division of Materials Science
National Univ. of Quilmes/CONICET, Bernal (Argentina)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

By applying nonadiabatic excited-state molecular dynamics, we investigate excitation energy transfer and exciton localization dynamics in a chlorophyll a (Chla) dimer system at the interface of two monomers of light-harvesting complex II trimer. After its optical excitation at the red edge of the Soret (B) band, the Chla dimer experiences an ultrafast intra- and intermolecular nonradiative relaxation process to the lowest band (Q_y). The energy relaxation is found to run faster in the Chla dimer than in the Chla monomer. Once the molecular system reaches the lowest Q_y band composed of two lowest excited states S₁ and S₂, the concluding relaxation step involves the S₂ → S₁ population transfer, resulting in a relatively slower relaxation rate. The strength of thermal fluctuations exceeds intraband electronic coupling between the states belonging to a certain band (B, Q_x, and Q_y), producing localized states on individual chromophores. Therefore, time evolution of spatial electronic localization during internal conversion reveals transient trapping on one of the Chla monomers participating in the events of intermonomeric energy exchange. In the phase space domains where electronic states are strongly coupled, these states become nearly degenerate promoting Frenkel-exciton-like delocalization and interchromophore energy transfer. As energy relaxation occurs, redistribution of the transition density on two Chla monomers leads to nearly equal distribution of the exciton among the molecules. For a single Chla, our analysis of excitonic dynamics reveals wave function amplitude transfer from nitrogen and outer carbon atoms to inner carbon atoms during non-radiative relaxation.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Research Foundation (NRF) (Singapore); Ministry of Education (Singapore); National Scientific and Technical Research Council (CONICET) (Argentina); National Agency for Scientific and Technological Promotion (ANPCyT) (Argentina)

Grant/Contract Number:: AC52-06NA25396; NRF-CRP5-2009-04; RG106/15; PICT-2014-2662

OSTI ID:: 1460648

Report Number(s):: LA-UR-17-21993; TRN: US1901887

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 121, Issue 21; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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