Ultrafast charge transfer in a nonfullerene all-small-molecule organic solar cell: a nonadiabatic dynamics simulation with optimally tuned range-separated functional

Abstract

Herein, we have employed LR-TDDFT-based nonadiabatic dynamics simulations to investigate the ultrafast charge transfer in a nonfullerene all-small-molecule donor-acceptor (D-A) system formed by a porphyrin small-molecule donor ZnP and a...

Nonadiabatic Dynamics Simulations for Photoinduced Processes in Molecules and Semiconductors: Methodologies and Applications

“…322−324 The combination of the OT-RSH functional and NAMD method was used to investigate the ultrafast charge transfer in a nonfullerene allsmall-molecule donor−acceptor system formed by a porphyrin small-molecule donor ZnP and a recently developed nonfullerene small-molecule acceptor 6TIC. 325 Our results indicated that the obtained results are less sensitive to the selected range separated hybrid functionals used for optimization. Moreover, such methods can provide even more reasonable results compared to the untuned ones.…”

“…The OT-RSH method depends on the nonempirical optimization of the range-separation parameter ω in the range-separated functionals so that a fundamental property that the exact functional must obey in exact Kohn–Sham (KS) or generalized KS (GKS) theory is fulfilled: that is, for an N-electron system, the negative of the HOMO energy − ε HOMO (N) must be equal to the molecular vertical IP­(N). Thus, these OT-RSH functionals can predict the excited state properties of various molecular systems effectively, and have witnessed great successes in fields ranging from OSCs to thermally activated delayed fluorescence (TADFs). − The combination of the OT-RSH functional and NAMD method was used to investigate the ultrafast charge transfer in a nonfullerene all-small-molecule donor–acceptor system formed by a porphyrin small-molecule donor ZnP and a recently developed nonfullerene small-molecule acceptor 6TIC . Our results indicated that the obtained results are less sensitive to the selected range separated hybrid functionals used for optimization.…”

Solvent effects on the photoinduced charge separation dynamics of directly linked zinc phthalocyanine-perylenediimide dyads: a nonadiabatic dynamics simulation with an optimally tuned screened range-separated hybrid functional

“…Therefore, the NAMD simulations in this work were performed with classical path approximation, which has been demonstrated to work very well for describing excited-state relaxation without involving large conformational change and bond forming or -breaking. 84,86,87,[91][92][93] Since ZnPc-PDI dyads exhibit rigid structures and no bond forming or breaking is involved as suggested by previous experimental work, 74 the classical path approximation is very suitable for this system.…”

“…This Considering the significant differences in results between the gas phase and benzonitrile, it is crucial to further validate the reliability of the excited state calculation method adopting the OT-SRSH-PCM functional used in this work. While previous studies have shown that tuning the o parameter can provide accurate results for the gas phase, [59][60][61][62][63]74 we decided to perform more tests to demonstrate the importance of tuning the b parameter for the calculations in benzonitrile. To this end, we conducted two additional excited state calculations using the same structure, the same PCM solvent model using benzonitrile as the solvent, and functional, but different o and b parameters.…”

“…Moreover, most applications are focused on the static electronic structure and rate constant calculations, while the nonadiabatic dynamics simulation was absent until we published our recent work. 74 In the present work, we adopted the OT-RSH and OT-SRSH-PCM functionals in LR-TDDFT based nonadiabatic dynamics simulations to explore the excited state dynamics of directly linked ZnPc-PDI dyads in the gas phase and benzonitrile. It is found that the solvent effects indeed have significant influences on the photoinduced dynamics of the ZnPc-PDI dyads.…”