PMID- 33380075
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20201231
IS  - 1089-7690 (Electronic)
IS  - 0021-9606 (Linking)
VI  - 153
IP  - 24
DP  - 2020 Dec 28
TI  - Exact description of excitonic dynamics in molecular aggregates weakly driven by 
      light.
PG  - 244122
LID - 10.1063/5.0029914 [doi]
AB  - We present a rigorous theoretical description of excitonic dynamics in molecular 
      light-harvesting aggregates photoexcited by weak-intensity radiation of arbitrary 
      properties. While the interaction with light is included up to the second order, 
      the treatment of the excitation-environment coupling is exact and results in an 
      exact expression for the reduced excitonic density matrix that is manifestly 
      related to the spectroscopic picture of the photoexcitation process. This 
      expression takes fully into account the environmental reorganization processes 
      triggered by the two interactions with light. This is particularly important for 
      slow environments and/or strong excitation-environment coupling. Within the 
      exponential decomposition scheme, we demonstrate how our result can be recast as 
      the hierarchy of equations of motion (HEOM) that explicitly and consistently 
      includes the photoexcitation step. We analytically describe the environmental 
      reorganization dynamics triggered by a delta-like excitation of a single 
      chromophore and demonstrate how our HEOM, in appropriate limits, reduces to the 
      Redfield equations comprising a pulsed photoexcitation and the nonequilibrium 
      Forster theory. We also discuss the relation of our formalism to the combined 
      Born-Markov-HEOM approaches in the case of excitation by thermal light.
FAU - Jankovic, Veljko
AU  - Jankovic V
AUID- ORCID: 0000000202972167
AD  - Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 121 16 
      Prague 2, Czech Republic.
FAU - Mancal, Tomas
AU  - Mancal T
AUID- ORCID: 0000000317363054
AD  - Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 121 16 
      Prague 2, Czech Republic.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Phys
JT  - The Journal of chemical physics
JID - 0375360
SB  - IM
EDAT- 2021/01/01 06:00
MHDA- 2021/01/01 06:01
CRDT- 2020/12/31 05:17
PHST- 2020/12/31 05:17 [entrez]
PHST- 2021/01/01 06:00 [pubmed]
PHST- 2021/01/01 06:01 [medline]
AID - 10.1063/5.0029914 [doi]
PST - ppublish
SO  - J Chem Phys. 2020 Dec 28;153(24):244122. doi: 10.1063/5.0029914.