Indirect Intersystem Crossing (S1 → T3/T2 → T1) Promoted by the Jahn-Teller Effect in Cycloparaphenylenes

Vennapusa Sivaranjana Reddy; S. Irle

doi:10.1021/acs.jctc.7b00166

Indirect Intersystem Crossing (S₁ → T₃/T₂ → T₁) Promoted by the Jahn-Teller Effect in Cycloparaphenylenes

Vennapusa Sivaranjana Reddy, S. Irle

Computational Chemistry and Nanomaterial

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Vibronic-coupling effects play a key role for excited-state charge- and energy-transfer processes in organic molecular systems. Here, we demonstrate how the Jahn-Teller effect in triplet excited states of highly symmetric cycloparaphenylenes triggers an indirect intersystem crossing deactivation pathway. Strong Jahn-Teller distortion in the doubly degenerate second excited triplet state (T₂) brings the molecular system energetically close to the lowest triplet state (T₁), thereby opening the possibility for an extremely rapid internal conversion. Quantum dynamics simulations reveal an initial T₂ → T₁ population decay within 50 fs. Experimental observation of size-dependent intersystem crossing rates of cycloparaphenylenes is explained based on the proposed S₁ → T₃/T₂ → T₁ mechanism.

Original language	English
Pages (from-to)	4944-4949
Number of pages	6
Journal	Journal of Chemical Theory and Computation
Volume	13
Issue number	10
DOIs	https://doi.org/10.1021/acs.jctc.7b00166
State	Published - Oct 10 2017

Funding

This work was partially supported by a CREST (Core Research for Evolutional Science and Technology) grant from JST. Calculations were performed in part at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, National Institutes for Natural Sciences. V.S.R. thanks Kai Welke (Nagoya University) for valuable suggestions.

Funders	Funder number
Japan Science and Technology Agency
Core Research for Evolutional Science and Technology

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abstract = "Vibronic-coupling effects play a key role for excited-state charge- and energy-transfer processes in organic molecular systems. Here, we demonstrate how the Jahn-Teller effect in triplet excited states of highly symmetric cycloparaphenylenes triggers an indirect intersystem crossing deactivation pathway. Strong Jahn-Teller distortion in the doubly degenerate second excited triplet state (T2) brings the molecular system energetically close to the lowest triplet state (T1), thereby opening the possibility for an extremely rapid internal conversion. Quantum dynamics simulations reveal an initial T2 → T1 population decay within 50 fs. Experimental observation of size-dependent intersystem crossing rates of cycloparaphenylenes is explained based on the proposed S1 → T3/T2 → T1 mechanism.",

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AB - Vibronic-coupling effects play a key role for excited-state charge- and energy-transfer processes in organic molecular systems. Here, we demonstrate how the Jahn-Teller effect in triplet excited states of highly symmetric cycloparaphenylenes triggers an indirect intersystem crossing deactivation pathway. Strong Jahn-Teller distortion in the doubly degenerate second excited triplet state (T2) brings the molecular system energetically close to the lowest triplet state (T1), thereby opening the possibility for an extremely rapid internal conversion. Quantum dynamics simulations reveal an initial T2 → T1 population decay within 50 fs. Experimental observation of size-dependent intersystem crossing rates of cycloparaphenylenes is explained based on the proposed S1 → T3/T2 → T1 mechanism.

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Indirect Intersystem Crossing (S₁ → T₃/T₂ → T₁) Promoted by the Jahn-Teller Effect in Cycloparaphenylenes

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