PMID- 37750240 OWN - NLM STAT- MEDLINE DCOM- 20231005 LR - 20231005 IS - 1463-9084 (Electronic) IS - 1463-9076 (Linking) VI - 25 IP - 38 DP - 2023 Oct 4 TI - Excitation energy equilibration in a trimeric LHCII complex involves unusual pathways. PG - 26360-26369 LID - 10.1039/d3cp02836d [doi] AB - We explore the energy equilibration within the LHCII trimer using various approaches, including the Redfield-Forster method (with different compartmentalization schemes) and the exact hierarchical equation of motion (HEOM). We demonstrate that the inter-monomeric migration in the trimeric LHCII complex is not limited to direct transfers between quasi-equilibrated chlorophylls (Chls) a, but also involves additional pathways with uphill transfers from Chls a to the stromal-side Chls b (connecting the Chls a clusters from different monomeric subunits). Although these uphill transfers are slow they still can increase the total rate of inter-monomeric transfers by a factor of 1.5. The same stromal-side Chls b also promote a depopulation of the Chl a604 long-lived state (blue-shifted and mixed with the lumenal-side Chls b). Due to the connection between the stromal- and lumenal-side Chls b clusters the intra- and inter-monomeric transfers from a604 to the main Chls a become faster by a factor of 1.6 and 1.75, respectively. FAU - Novoderezhkin, Vladimir I AU - Novoderezhkin VI AUID- ORCID: 0000-0003-4583-5725 AD - A. N. Belozersky Institute of Physico-Chemical Biology, Lomonosov Moscow State University, Leninskie Gory, 119992, Moscow, Russia. v.novoderezhkin@gmail.com. LA - eng PT - Journal Article DEP - 20231004 PL - England TA - Phys Chem Chem Phys JT - Physical chemistry chemical physics : PCCP JID - 100888160 RN - 0 (Light-Harvesting Protein Complexes) RN - 1406-65-1 (Chlorophyll) SB - IM MH - *Light-Harvesting Protein Complexes/metabolism MH - Energy Transfer MH - Physical Phenomena MH - *Chlorophyll MH - Kinetics EDAT- 2023/09/26 06:43 MHDA- 2023/10/05 06:43 CRDT- 2023/09/26 04:32 PHST- 2023/10/05 06:43 [medline] PHST- 2023/09/26 06:43 [pubmed] PHST- 2023/09/26 04:32 [entrez] AID - 10.1039/d3cp02836d [doi] PST - epublish SO - Phys Chem Chem Phys. 2023 Oct 4;25(38):26360-26369. doi: 10.1039/d3cp02836d.