Signatures of Conical Intersection Dynamics in the Time-Resolved Photoelectron Spectrum of Furan: Theoretical Modeling with an Ensemble Density Functional Theory Method
Abstract
The non-adiabatic dynamics of furan excited in the ππ* state (S₂ in the Franck–Condon geometry) was studied using non-adiabatic molecular dynamics simulations in connection with an ensemble density functional method. The time-resolved photoelectron spectra were theoretically simulated in a wide range of electron binding energies that covered the valence as well as the core electrons. The dynamics of the decay (rise) of the photoelectron signal were compared with the excited-state population dynamics. It was observed that the photoelectron signal decay parameters at certain electron binding energies displayed a good correlation with the events occurring during the excited-state dynamics. Thus, the time profile of the photoelectron intensity of the K-shell electrons of oxygen (decay constant of 34 ± 3 fs) showed a reasonable correlation with the time of passage through conical intersections with the ground state (47 ± 2 fs). The ground-state recovery constant of the photoelectron signal (121 ± 30 fs) was in good agreement with the theoretically obtained excited-state lifetime (93 ± 9 fs), as well as with the experimentally estimated recovery time constant (ca. 110 fs). Hence, it is proposed to complement the traditional TRPES observations with the trXPS (or trNEXAFS) measurements to obtain more reliable estimates of the most mechanistically important events during the excited-state dynamics.
Additional Information
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). Received: 30 March 2021 / Revised: 13 April 2021 / Accepted: 15 April 2021 / Published: 20 April 2021. (This article belongs to the Special Issue Ultrafast non-Adiabatic Processes in Molecules: Recent Advances in Theory and Experiment) Author Contributions. Conceptualization, M.F. and C.-H.C.; methodology, M.F.; software, M.F., S.L., and H.N.; validation, M.F., S.L., and H.N.; formal analysis, M.F. and C.-H.C.; writing—original draft preparation, M.F.; writing—review and editing, M.F. and C.-H.C.; funding acquisition, C.-H.C. and M.F. All authors have read and agreed to the published version of the manuscript. This research was funded by the National Research Foundation of Korea (NRF), grant number 2019H1D3A2A02102948 (M.F.) and grant numbers 2020R1A2C2008246 and 2020R1A5A1019141 (C.-H.C.), as well as by the Samsung Science and Technology Foundations, grant number SSTF-BA1701-12 (C.-H.C.). Institutional Review Board Statement: Not applicable. Informed Consent Statement: Not applicable. Data Availability Statement: Not applicable. The authors declare no conflict of interest.Attached Files
Published - ijms-22-04276-v2.pdf
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Additional details
- PMCID
- PMC8074317
- Eprint ID
- 108950
- Resolver ID
- CaltechAUTHORS:20210503-155515372
- 2019H1D3A2A02102948
- National Research Foundation of Korea
- 2020R1A2C2008246
- National Research Foundation of Korea
- 2020R1A5A1019141
- National Research Foundation of Korea
- SSTF-BA1701-12
- Samsung Science and Technology Foundation
- Created
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2021-05-04Created from EPrint's datestamp field
- Updated
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2023-07-18Created from EPrint's last_modified field