التفاصيل البيبلوغرافية
| العنوان: |
How Can We Predict Accurate Electrochromic Shifts for Biochromophores? A Case Study on the Photosynthetic Reaction Center |
| المؤلفون: |
Abhishek Sirohiwal (5368541), Frank Neese (736441), Dimitrios A. Pantazis (1498477) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Molecular Biology, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, RC chromophores, range-separated DFT methods, site energy distribution, excitation energy transfer, DLPNO, RC site energy shifts, SCS, LC-BLYP, understanding photosynthetic systems, DLPNO-STEOM-CCSD, PSII, STEOM-CCSD, X-V, functional, Photosynthetic Reaction Center Prot., core protein organization, 3LYP, charge separation, CC, ADC, TD-DFT, electrochromic shifts, quantum chemical methods, SOS |
| الوصف: |
Protein-embedded chromophores are responsible for light harvesting, excitation energy transfer, and charge separation in photosynthesis. A critical part of the photosynthetic apparatus are reaction centers (RCs), which comprise groups of (bacterio)chlorophyll and (bacterio)pheophytin molecules that transform the excitation energy derived from light absorption into charge separation. The lowest excitation energies of individual pigments (site energies) are key for understanding photosynthetic systems, and form a prime target for quantum chemistry. A major theoretical challenge is to accurately describe the electrochromic (Stark) shifts in site energies produced by the inhomogeneous electric field of the protein matrix. Here, we present large-scale quantum mechanics/molecular mechanics calculations of electrochromic shifts for the RC chromophores of photosystem II (PSII) using various quantum chemical methods evaluated against the domain-based local pair natural orbital (DLPNO) implementation of the similarity-transformed equation of motion coupled cluster theory with single and double excitations (STEOM-CCSD). We show that certain range-separated density functionals (ωΒ97, ωΒ97X-V, ωΒ2PLYP, and LC-BLYP) correctly reproduce RC site energy shifts with time-dependent density functional theory (TD-DFT). The popular CAM-B3LYP functional underestimates the shifts and is not recommended. Global hybrid functionals are too insensitive to the environment and should be avoided, while nonhybrid functionals are strictly nonapplicable. Among the applicable approximate coupled cluster methods, the canonical versions of CC2 and ADC(2) were found to deviate significantly from the reference results both for the description of the lowest excited state and for the electrochromic shifts. By contrast, their spin-component-scaled (SCS) and particularly the scale-opposite-spin (SOS) variants compare well with the reference DLPNO-STEOM-CCSD and the best range-separated DFT methods. The emergence of RC excitation asymmetry is discussed ... |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/How_Can_We_Predict_Accurate_Electrochromic_Shifts_for_Biochromophores_A_Case_Study_on_the_Photosynthetic_Reaction_Center/13865010 |
| DOI: |
10.1021/acs.jctc.0c01152.s001 |
| الاتاحة: |
https://doi.org/10.1021/acs.jctc.0c01152.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.D02E2E65 |
| قاعدة البيانات: |
BASE |