Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer
Abstract The transfer of population between two intersecting quantum states is the most fundamental event in many dynamical processes in physics, chemistry, biology, and material science. Any two-state description of such processes requires population leaving one state to instantaneously appear in t...
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Nature Portfolio
2025-08-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-62162-6 |
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| author | Danylo T. Matselyukh Florian Rott Thomas Schnappinger Pengju Zhang Zheng Li Jeremy O. Richardson Regina de Vivie-Riedle Hans Jakob Wörner |
| author_facet | Danylo T. Matselyukh Florian Rott Thomas Schnappinger Pengju Zhang Zheng Li Jeremy O. Richardson Regina de Vivie-Riedle Hans Jakob Wörner |
| author_sort | Danylo T. Matselyukh |
| collection | DOAJ |
| description | Abstract The transfer of population between two intersecting quantum states is the most fundamental event in many dynamical processes in physics, chemistry, biology, and material science. Any two-state description of such processes requires population leaving one state to instantaneously appear in the other. We show that coupling to additional states, present in all real-world systems, can cause a measurable delay in population transfer. Using attosecond spectroscopy supported by quantum-chemical calculations, we measure a delay of 1.46 ± 0.41 fs at a charge-transfer crossing in CF3I+, where an electron hole moves from the fluorine atoms to iodine. Our measurements also resolve the other fundamental quantum-dynamical processes involved in the charge-transfer reaction: a vibrational rearrangement time of 9.38 ± 0.21 fs (during which the vibrational wave packet travels to the state crossing) and a population-transfer time of 2.3–2.4 fs. Our work shows that delays in population transfer readily appear in otherwise-adiabatic reactions and predicts them to be on the order of a single-femtosecond for molecular valence-state crossings. These results have implications for many research areas, such as atomic and molecular physics, charge transfer, or light harvesting. |
| format | Article |
| id | doaj-art-ebb1a894543948aca94f19058836b51a |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-ebb1a894543948aca94f19058836b51a2025-08-20T03:43:27ZengNature PortfolioNature Communications2041-17232025-08-011611810.1038/s41467-025-62162-6Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transferDanylo T. Matselyukh0Florian Rott1Thomas Schnappinger2Pengju Zhang3Zheng Li4Jeremy O. Richardson5Regina de Vivie-Riedle6Hans Jakob Wörner7Department of Chemistry and Applied Biosciences, ETH ZürichDepartment of Chemistry, LMU MunichDepartment of Chemistry, LMU MunichDepartment of Chemistry and Applied Biosciences, ETH ZürichSchool of Physics, Peking UniversityDepartment of Chemistry and Applied Biosciences, ETH ZürichDepartment of Chemistry, LMU MunichDepartment of Chemistry and Applied Biosciences, ETH ZürichAbstract The transfer of population between two intersecting quantum states is the most fundamental event in many dynamical processes in physics, chemistry, biology, and material science. Any two-state description of such processes requires population leaving one state to instantaneously appear in the other. We show that coupling to additional states, present in all real-world systems, can cause a measurable delay in population transfer. Using attosecond spectroscopy supported by quantum-chemical calculations, we measure a delay of 1.46 ± 0.41 fs at a charge-transfer crossing in CF3I+, where an electron hole moves from the fluorine atoms to iodine. Our measurements also resolve the other fundamental quantum-dynamical processes involved in the charge-transfer reaction: a vibrational rearrangement time of 9.38 ± 0.21 fs (during which the vibrational wave packet travels to the state crossing) and a population-transfer time of 2.3–2.4 fs. Our work shows that delays in population transfer readily appear in otherwise-adiabatic reactions and predicts them to be on the order of a single-femtosecond for molecular valence-state crossings. These results have implications for many research areas, such as atomic and molecular physics, charge transfer, or light harvesting.https://doi.org/10.1038/s41467-025-62162-6 |
| spellingShingle | Danylo T. Matselyukh Florian Rott Thomas Schnappinger Pengju Zhang Zheng Li Jeremy O. Richardson Regina de Vivie-Riedle Hans Jakob Wörner Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer Nature Communications |
| title | Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer |
| title_full | Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer |
| title_fullStr | Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer |
| title_full_unstemmed | Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer |
| title_short | Attosecond spectroscopy of molecular charge transfer uncovers a 1.5-fs delay in population transfer |
| title_sort | attosecond spectroscopy of molecular charge transfer uncovers a 1 5 fs delay in population transfer |
| url | https://doi.org/10.1038/s41467-025-62162-6 |
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