PMID- 32877177
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20201013
IS  - 1549-9626 (Electronic)
IS  - 1549-9618 (Linking)
VI  - 16
IP  - 10
DP  - 2020 Oct 13
TI  - Simulating Absorption Spectra of Multiexcitonic Systems via Quasiclassical 
      Mapping Hamiltonian Methods.
PG  - 6465-6480
LID - 10.1021/acs.jctc.0c00709 [doi]
AB  - In this paper, we compare the ability of different quasiclassical mapping 
      Hamiltonian methods to accurately simulate the absorption spectra of 
      multiexcitonic molecular systems. Two distinctly different approaches for 
      simulating the absorption spectra are considered: (1) a perturbative approach, 
      which relies on the first-order perturbation theory with respect to the 
      field-matter interaction; (2) a nonperturbative approach, which mimics the 
      experimental measurement of the absorption spectra from the free-induction decay 
      that follows a short laser pulse. The methods compared are several variations of 
      the linearized semiclassical (LSC) method, the symmetrical quasiclassical (SQC) 
      method, and the mean-field (Ehrenfest) method. The comparison is performed in the 
      context of a biexcitonic model and a seven-excitonic model of the 
      Fenna-Matthews-Olson (FMO) complex. The accuracy of the various methods is tested 
      by comparing their predictions to the quantum-mechanically exact results obtained 
      via the hierarchy of the equations of motion (HEOM) method, as well as to the 
      results based on the Redfield quantum master equation. The results show that the 
      LSC-based quasiclassical mapping Hamiltonian methods can yield the accurate and 
      robust absorption spectra in the high-temperature and/or slow-bath limit, where 
      the nuclear degrees of freedom can be treated as classical.
FAU - Gao, Xing
AU  - Gao X
AD  - Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, 
      United States.
FAU - Lai, Yifan
AU  - Lai Y
AD  - Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, 
      United States.
FAU - Geva, Eitan
AU  - Geva E
AUID- ORCID: 0000-0002-7935-4586
AD  - Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, 
      United States.
LA  - eng
PT  - Journal Article
DEP - 20200921
PL  - United States
TA  - J Chem Theory Comput
JT  - Journal of chemical theory and computation
JID - 101232704
SB  - IM
EDAT- 2020/09/03 06:00
MHDA- 2020/09/03 06:01
CRDT- 2020/09/03 06:00
PHST- 2020/09/03 06:00 [pubmed]
PHST- 2020/09/03 06:01 [medline]
PHST- 2020/09/03 06:00 [entrez]
AID - 10.1021/acs.jctc.0c00709 [doi]
PST - ppublish
SO  - J Chem Theory Comput. 2020 Oct 13;16(10):6465-6480. doi: 
      10.1021/acs.jctc.0c00709. Epub 2020 Sep 21.