Higher-Energy
Charge Transfer States Facilitate Charge Separation in Donor–Acceptor
Molecular Dyads
Version 3 2018-05-19, 13:13
Version 2 2017-06-22, 14:15
Version 1 2017-06-08, 20:03
Posted on 2018-05-19 - 13:13
We simulate subpicosecond charge
separation in two donor–acceptor
molecular dyads. Charge separation dynamics is described using a quantum
master equation, with parameters of the dyad Hamiltonian obtained
from density functional theory (DFT) and time-dependent density functional
theory (TDDFT) calculations and the rate of energy dissipation estimated
from Ehrenfest-TDDFT molecular dynamics simulations. We find that
higher-energy charge transfer states must be included in the dyad
Hamiltonian in order to obtain agreement of charge separation rates
with the experimental values. Our results show that efficient and
irreversible charge separation involves both coherent electron transfer
from the donor excited state to higher-energy unoccupied states on
the acceptor and incoherent energy dissipation that relaxes the dyad
to the lowest energy charge transfer state. The role of coherence
depends on the initial excited state, with electron delocalization
within Hamiltonian eigenstates found to be more important than coherence
between eigenstates. We conclude that ultrafast charge separation
is most likely to occur in donor–acceptor dyads possessing
dense manifolds of charge transfer states at energies close to those
of Frenkel excitons on the donor, with strong couplings to these states
enabling partial delocalization of eigenstates over acceptor and donor.
CITE THIS COLLECTION
DataCite
3 Biotech
3D Printing in Medicine
3D Research
3D-Printed Materials and Systems
4OR
AAPG Bulletin
AAPS Open
AAPS PharmSciTech
Abhandlungen aus dem Mathematischen Seminar der Universität Hamburg
ABI Technik (German)
Academic Medicine
Academic Pediatrics
Academic Psychiatry
Academic Questions
Academy of Management Discoveries
Academy of Management Journal
Academy of Management Learning and Education
Academy of Management Perspectives
Academy of Management Proceedings
Academy of Management Review
Lee, Donghyun; Forsuelo, Michael A.; Kocherzhenko, Aleksey A.; Whaley, K. Birgitta (2017). Higher-Energy
Charge Transfer States Facilitate Charge Separation in Donor–Acceptor
Molecular Dyads. ACS Publications. Collection. https://doi.org/10.1021/acs.jpcc.7b03197
or
Select your citation style and then place your mouse over the citation text to select it.
SHARE
Usage metrics
Read the peer-reviewed publication
AUTHORS (4)
DL
Donghyun Lee
MF
Michael A. Forsuelo
AK
Aleksey A. Kocherzhenko
KW
K. Birgitta Whaley
KEYWORDS
higher-energy charge transfer statesHigher-Energy Charge Transfer States Facilitate Charge Separationcharge separation dynamicsquantum master equationultrafast charge separationcharge separation ratesenergy dissipationenergy charge transfer statesubpicosecond charge separationdonoreigenstatecharge transfer statesDFTTDDFTdyad