Stabilization of Charge-Transfer Excited States in Biological Systems: A Computational Focus on the Special Pair in Photosystem II Reaction Centers

Forde, Aaron; Maity, Sayan; Freixas Lemus, Victor Manuel; Fernandez-Alberti, Sebastian; Neukirch, Amanda J.; Kleinekathöfer, Ulrich; Tretiak, Sergei

doi:10.1021/acs.jpclett.4c00362

Title: Stabilization of Charge-Transfer Excited States in Biological Systems: A Computational Focus on the Special Pair in Photosystem II Reaction Centers

Journal Article · 08 April 2024 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.4c00362 · OSTI ID:2340917

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States). Center for Nonlinear Studies (CNLS)
Constructor Univ., Bremen (Germany)
Universidad Nacional de Quilmes, Bernal (Argentina); National Scientific and Technical Research Council (CONICET) (Argentina)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
School of Science, Constructor University, Campus Ring 1, 28759 Bremen, Germany
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)

Charge-transfer (CT) excited states play an important role in many biological processes. However, many computational approaches often inadequately address the equilibration effects of nuclear and environmental degrees of freedom on these states. One prominent example of systems in which CT states are of utmost importance is reaction centers (RC) in photosystems. Here we use a multiscale approach combined with time-dependent density functional theory to explore the lowest CT excited state of the special pair P_D1–P_D2 in the Photosystem II-RC of a cyanobacterium. We find that the nonequilibrium CT excited state resides near the Soret band, making an exciton the lowest-energy excited state. However, accounting for nuclear and state-specific dielectric equilibration along the CT potential energy surface (PES), the CT state P_D1^––P_D2⁺ stabilizes energetically below the excitonic state. Importantly, this underscores the crucial role of state-specific solvation in mapping the PES of CT states, as demonstrated in a simplified dimer model.

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

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2340917

Report Number(s):: LA-UR--24-20860

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 15 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrical properties
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excitons
insulators
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