Bifurcation of excited state trajectories toward energy transfer or electron transfer directed by wave function symmetry
- 18 January 2021
- journal article
- research article
- Published by Proceedings of the National Academy of Sciences in Proceedings of the National Academy of Sciences of the United States of America
- Vol. 118 (4)
- https://doi.org/10.1073/pnas.2018521118
Abstract
This work explores the concept that differential wave function overlap between excited states can be engineered within a molecular chromophore. The aim is to control excited state wave function symmetries, so that symmetry matches or mismatches result in differential orbital overlap and define low-energy trajectories or kinetic barriers within the excited state surface, that drive excited state population toward different reaction pathways. Two donor–acceptor assemblies were explored, where visible light absorption prepares excited states of different wave function symmetry. These states could be resolved using transient absorption spectroscopy, thanks to wave function symmetry-specific photoinduced optical transitions. One of these excited states undergoes energy transfer to the acceptor, while another undertakes a back-electron transfer to restate the ground state. This differential behavior is possible thanks to the presence of kinetic barriers that prevent excited state equilibration. This strategy can be exploited to avoid energy dissipation in energy conversion or photoredox catalytic schemes.Funding Information
- Universidad de Buenos Aires (UBACyT 20020130100534BA)
- Consejo Nacional de Investigaciones Científicas y Técnicas (PIP 112-20150100394CO)
- MINCyT | Agencia Nacional de Promoción Científica y Tecnológica (PICT 2013 00069)
- MINCyT | Agencia Nacional de Promoción Científica y Tecnológica (PICT 2018-00924)
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