TY - JOUR
T1 - Simulating the Coupled Structural-Electronic Dynamics of Photoexcited Lead Iodide Perovskites
AU - Uratani, Hiroki
AU - Nakai, Hiromi
AU - Nakai, Hiromi
AU - Nakai, Hiromi
N1 - Funding Information:
This study was financially supported by the Japan Society for Promotion of Science (JSPS) Grant-in-Aid for Scientific Research (S) No. 18H05264 and Grant-in-Aid for JSPS Research Fellow No. 18J21325. We also acknowledge the support by the Ministry of Education, Culture, Sports, Science and Technology, Japan, as “Priority Issue on Post-K Computer” (Development of new fundamental technologies for high-efficiency energy creation, conversion/storage, and use). The computational resources were provided by Research Center for Computational Science, National Institutes of Natural Sciences, Okazaki, Japan. H.U. is indebted to the Research Fellowship for Young Scientists from JSPS.
Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/6/4
Y1 - 2020/6/4
N2 - Motivated by the optoelectronic applications of lead halide perovskites (LHPs), researchers have paid considerable attention to their photoexcited-state dynamics, where the coupling between the electronic and nuclear dynamics is pronounced. Here, we present simulations of the photoexcited-state dynamics of representative lead iodide perovskites, CsPbI3 and MAPbI3 (MA = CH3NH3), by adopting nonadiabatic molecular dynamics combined with the linear-response time-dependent density-functional tight-binding (LR-TD-DFTB) method, an efficient excited-state calculation framework. In the calculations, the electronic wave function and the nuclear coordinates were propagated in a mutually dependent manner. The results suggest that the excited LHPs undergo exciton dissociation, hot carrier cooling, and polaron formation on similar time scales. In particular, the decay of the carrier energy is attributed to not only the relaxation toward the band edge but also the change in orbital energy originating from the structural deformation, highlighting the importance of coupling between the electronic and nuclear degrees of freedom.
AB - Motivated by the optoelectronic applications of lead halide perovskites (LHPs), researchers have paid considerable attention to their photoexcited-state dynamics, where the coupling between the electronic and nuclear dynamics is pronounced. Here, we present simulations of the photoexcited-state dynamics of representative lead iodide perovskites, CsPbI3 and MAPbI3 (MA = CH3NH3), by adopting nonadiabatic molecular dynamics combined with the linear-response time-dependent density-functional tight-binding (LR-TD-DFTB) method, an efficient excited-state calculation framework. In the calculations, the electronic wave function and the nuclear coordinates were propagated in a mutually dependent manner. The results suggest that the excited LHPs undergo exciton dissociation, hot carrier cooling, and polaron formation on similar time scales. In particular, the decay of the carrier energy is attributed to not only the relaxation toward the band edge but also the change in orbital energy originating from the structural deformation, highlighting the importance of coupling between the electronic and nuclear degrees of freedom.
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U2 - 10.1021/acs.jpclett.0c01028
DO - 10.1021/acs.jpclett.0c01028
M3 - Article
C2 - 32418430
AN - SCOPUS:85085962445
SN - 1948-7185
VL - 11
SP - 4448
EP - 4455
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 11
ER -