PMID- 34353023
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20210819
IS  - 1520-5215 (Electronic)
IS  - 1089-5639 (Linking)
VI  - 125
IP  - 32
DP  - 2021 Aug 19
TI  - Strong Exciton-Vibrational Coupling in Molecular Assemblies. Dynamics Using the 
      Polaron Transformation in HEOM Space.
PG  - 7052-7065
LID - 10.1021/acs.jpca.1c02684 [doi]
AB  - In Frenkel exciton dynamics of aggregated molecules, the polaron transformation 
      (PT) technique leads to decoupling of diagonal elements in the subspace of 
      excited electronic states from vibrations. In this article we describe for the 
      first time how PT becomes applicable in the framework of the "Hierarchical 
      Equations of Motion" (HEOM) approach for treatment of open quantum systems. We 
      extend the concept of formulating operators in HEOM space by deriving 
      hierarchical equations of PT which lead to a shift in the excited state potential 
      energy surface to compensate its displacement. While the assumption of thermal 
      equilibration of the vibrational oscillators, introduced by PT, results in a 
      stationary state in a monomer, in a dimer under the same assumption 
      nonequilibrium dynamics appears because of the interplay of the transfer process 
      and vibrational equilibration. Both vertical transitions generating a 
      vibrationally hot state and initially equilibrated vibrational oscillators evolve 
      toward the same stationary asymptotic state associated with polaron formation. 
      The effect of PT on the dynamics of this process depends on initial excitation 
      and basis representation of the electronic system. The developed approach 
      facilitates a generic formulation of quantum master equations involving 
      perturbative treatment of polaron dynamics.
FAU - Seibt, Joachim
AU  - Seibt J
AUID- ORCID: 0000-0001-5162-8883
AD  - Institute of Physics, University of Rostock, Albert-Einstein-Str. 23-24, 18059 
      Rostock, Germany.
AD  - Institute for Theoretical Physics, Johannes Kepler University Linz, Altenberger 
      Str. 69, 4040 Linz, Austria.
FAU - Kuhn, Oliver
AU  - Kuhn O
AUID- ORCID: 0000-0002-5132-2961
AD  - Institute of Physics, University of Rostock, Albert-Einstein-Str. 23-24, 18059 
      Rostock, Germany.
LA  - eng
PT  - Journal Article
DEP - 20210805
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
SB  - IM
EDAT- 2021/08/07 06:00
MHDA- 2021/08/07 06:01
CRDT- 2021/08/06 05:27
PHST- 2021/08/07 06:00 [pubmed]
PHST- 2021/08/07 06:01 [medline]
PHST- 2021/08/06 05:27 [entrez]
AID - 10.1021/acs.jpca.1c02684 [doi]
PST - ppublish
SO  - J Phys Chem A. 2021 Aug 19;125(32):7052-7065. doi: 10.1021/acs.jpca.1c02684. Epub 
      2021 Aug 5.