Hierarchical Equations of Motion Simulation of Temperature‐Dependent Two‐Dimensional Electronic Spectroscopy of the Chlorophyll a Manifold in LHCII. Issue 13 (2nd June 2020)

• Record Type: Journal Article
• Authors: Leng, Xuan; Do, Thanh Nhut; Akhtar, Parveen; Nguyen, Hoang Long; Lambrev, Petar H.; Tan, Howe‐Siang
• Is Part Of: Chemistry, an Asian journal. Volume 15:Issue 13(2020)
• Page Start: 1996
• Page End: 2004
• Publication Date: 2020-06-02
• Subjects: Light-harvesting complexes -- Excitation energy transfer -- Multidimensional spectroscopy -- HEOM-PMA; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.202000467
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: We simulated two‐dimensional electronic spectra (2DES) of the chlorophyll a manifold of light‐harvesting complex II (LHCII) at various temperatures (77, 110, 150, 190, 230, 273, and 293 K) using the hierarchical equations of the motion‐phase matching approach. We confirm the main excitation energy transfer pathways assignments within the chlorophyll a manifold of LHCII measured in a recent work (J. Phys. Chem. B 2019, 123, 6765–6775). The calculated transfer rates are also in general agreement with the measured rates. We also provided theoretical confirmation for the experimental assignments, as uphill and downhill energy transfer processes, of 2D spectral features that were reported in recent experimental reports. These temperature‐dependent features were also ascertained to follow the detailed‐balance principle. Abstract : The Hierarchical Equations of Motion method was used to simulate temperature dependent two‐dimensional electronic spectra (2DES) of chlorophyll a energy transfer processes in LHCII. The simulation confirms previous experimental assignments of 2DES cross‐peaks corresponding to uphill and downhill energy transfer processes following the detailed balance condition.