21 November 2024
Issue 43
Page 17705 to 18208
Diverse quantum interference regimes in intramolecular singlet fission chromophores with thiophene-based linkers
An array of thiophene-based π-conjugated linkers in covalently linked pentacene dimers allow us to access diverse quantum interference (QI), modulating nonadiabatic coupling (NAC) in the singlet fission (SF) process. Simulations show that structural isomerism in terms of S atom orientation substantially alters NAC with relatively marginal impacts on energies. Extended curly arrow rules (ECARs) reveal sensitive dependence of QI on SF linker topologies and connectivity, categorizing regimes of constructive, destructive, and previously unrealized in SF research, shifted destructive QI. Drastic NAC changes in terms of S atom orientation are rationalized based on the nature of QI. Our results from nonequilibrium Green's function calculation using density functional theory corroborate the classification of QI regimes based on ECARs. Moreover, we found that the extent of charge resonance contribution in electronic states relevant to multiexciton formation and the appearance of optically allowed charge transfer excitation strongly depends on the operative QI regime. Notably, the magnitude of NAC effectively captures this influence. Our findings show that QI can rationalize and semi-quantitatively correlate with NAC for the multiexciton formation step in the SF process.
- Jonghwan Lee
- Sungsik Eom
- Hyungjun Kim
https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc03546a
RSC_Chemical science
21 November 2024
Issue 43
Page 17705 to 18208
Diverse quantum interference regimes in intramolecular singlet fission chromophores with thiophene-based linkers
An array of thiophene-based π-conjugated linkers in covalently linked pentacene dimers allow us to access diverse quantum interference (QI), modulating nonadiabatic coupling (NAC) in the singlet fission (SF) process. Simulations show that structural isomerism in terms of S atom orientation substantially alters NAC with relatively marginal impacts on energies. Extended curly arrow rules (ECARs) reveal sensitive dependence of QI on SF linker topologies and connectivity, categorizing regimes of constructive, destructive, and previously unrealized in SF research, shifted destructive QI. Drastic NAC changes in terms of S atom orientation are rationalized based on the nature of QI. Our results from nonequilibrium Green's function calculation using density functional theory corroborate the classification of QI regimes based on ECARs. Moreover, we found that the extent of charge resonance contribution in electronic states relevant to multiexciton formation and the appearance of optically allowed charge transfer excitation strongly depends on the operative QI regime. Notably, the magnitude of NAC effectively captures this influence. Our findings show that QI can rationalize and semi-quantitatively correlate with NAC for the multiexciton formation step in the SF process.
https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc03546a
Image created by minjeong Kim / Nanosphere