In:
Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC)
Kurzfassung:
Herein, we have employed the combination of the optimally tuned screened range-separated hybrid (OT-SRSH) functional, the polarizable continuum model (PCM), and nonadiabatic dynamics (NAMD) simulation to investigate the photoinduced dynamics of a directly linked donor-acceptor dyads formed by zinc phthalocyanine (ZnPc) and perylenediimide (PDI), in which ZnPc is the donor while PDI is the acceptor. Our simulations aim to analyze the behavior of these dyads upon local excitation of the ZnPc moiety in gas phase and in benzonitrile. Our findings indicate that the presence of a solvent can significantly influence the excited state dynamics of ZnPc-PDI dyads. Specifically, the polar solvent benzonitrile effectively lowers the vertical excitation energies of the charge transfer (CT) state from ZnPc to PDI. As a result, the energetic order of the locally excited (LE) states of ZnPc and the CT states is reversed compared to the gas phase. Consequently, the photoinduced electron transfer (PET) dynamics from ZnPc to PDI, which is absent in the gas phase, takes place in benzonitrile with a time constant of 10.4 ps. Importantly, our present work not only qualitatively agrees with experimental results but also provides in-depth insights into the underlying mechanisms responsible for the photoinduced dynamics of ZnPc-PDI. Moreover, this study emphasizes the importance of properly considering solvent effects in NAMD simulation of organic donor-acceptor systems, taking into account the distinct excited state dynamics observed in the gas phase and benzonitrile. Furthermore, the combination of the OTSRSH functional, the PCM solvent model, and nonadiabatic dynamics simulations shows promise as a strategy for investigating the complex excited state dynamics of organic donor-acceptor systems in solvents. These findings can be valuable for the future design of novel organic donor-acceptor structures with improved performance.
Materialart:
Online-Ressource
ISSN:
1463-9076
,
1463-9084
Sprache:
Englisch
Verlag:
Royal Society of Chemistry (RSC)
Publikationsdatum:
2023
ZDB Id:
1476283-3
ZDB Id:
1476244-4
ZDB Id:
1460656-2
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