Electronic Absorption and Circular Dichroism Spectra of One-Dimensional Bay-Substituted Chiral PDIs: Effects of Intermolecular Interactions, Vibronic Coupling, and Aggregate Size DOI

Yuchuan Xu,

Yi Zhao, WanZhen Liang

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(47), P. 20253 - 20263

Published: Nov. 13, 2024

Electronic circular dichroism (ECD) spectroscopy is the preferred tool for studying organic chiral supramolecules. However, it a great challenge to experimentally clarify contributions ECD spectra from molecular vibrational motions and intermolecular interactions, key factors an efficient system architecture design of chemical sensors, catalysts, or optoelectronics. Focusing on this issue, here, we perform theoretical studies vibrationally resolved absorption two one-dimensional bay-substituted perylene diimides (PDIs) by employing non-Markovian stochastic Schrödinger equation (NMSSE) with respect model Hamiltonian in diabatic representation, which includes intramolecular localized excited states (LEs), change-transfer (CTEs), vibronic couplings (VC) as well. Our calculated results exhibit that spectra, inclusion VC effect, agree better experimental ones than those without effect difference between traditional PDIs much less obvious their verifying sensitive absolute configuration conformation We further make comparison among pure electronic aggregates different aggregate sizes time-dependent density functional theory mixed exciton decoupling LE CTE states. It shown hybridization emergence new peaks troughs high-energy band significant deviation spectrum predicted chirality rule. oligomers odd–even alternation pattern changes size.

Language: Английский

Electronic Absorption and Circular Dichroism Spectra of One-Dimensional Bay-Substituted Chiral PDIs: Effects of Intermolecular Interactions, Vibronic Coupling, and Aggregate Size DOI

Yuchuan Xu,

Yi Zhao, WanZhen Liang

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(47), P. 20253 - 20263

Published: Nov. 13, 2024

Electronic circular dichroism (ECD) spectroscopy is the preferred tool for studying organic chiral supramolecules. However, it a great challenge to experimentally clarify contributions ECD spectra from molecular vibrational motions and intermolecular interactions, key factors an efficient system architecture design of chemical sensors, catalysts, or optoelectronics. Focusing on this issue, here, we perform theoretical studies vibrationally resolved absorption two one-dimensional bay-substituted perylene diimides (PDIs) by employing non-Markovian stochastic Schrödinger equation (NMSSE) with respect model Hamiltonian in diabatic representation, which includes intramolecular localized excited states (LEs), change-transfer (CTEs), vibronic couplings (VC) as well. Our calculated results exhibit that spectra, inclusion VC effect, agree better experimental ones than those without effect difference between traditional PDIs much less obvious their verifying sensitive absolute configuration conformation We further make comparison among pure electronic aggregates different aggregate sizes time-dependent density functional theory mixed exciton decoupling LE CTE states. It shown hybridization emergence new peaks troughs high-energy band significant deviation spectrum predicted chirality rule. oligomers odd–even alternation pattern changes size.

Language: Английский

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