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Signatures of Conical Intersection Dynamics in the Time-Resolved Photoelectron Spectrum of Furan: Theoretical Modeling with an Ensemble Density Functional Theory Method

Filatov, Michael and Lee, Seunghoon and Nakata, Hiroya and Choi, Cheol-Ho (2021) Signatures of Conical Intersection Dynamics in the Time-Resolved Photoelectron Spectrum of Furan: Theoretical Modeling with an Ensemble Density Functional Theory Method. International Journal of Molecular Sciences, 22 (8). Art. No. 4276. ISSN 1422-0067. PMCID PMC8074317. https://resolver.caltech.edu/CaltechAUTHORS:20210503-155515372

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.3390/ijms22084276DOIArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/pmc8074317/PubMed CentralArticle
ORCID:
AuthorORCID
Filatov, Michael0000-0002-1541-739X
Lee, Seunghoon0000-0003-3665-587X
Choi, Cheol-Ho0000-0002-8757-1396
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.
Funders:
Funding AgencyGrant Number
National Research Foundation of Korea2019H1D3A2A02102948
National Research Foundation of Korea2020R1A2C2008246
National Research Foundation of Korea2020R1A5A1019141
Samsung Science and Technology FoundationSSTF-BA1701-12
Subject Keywords:non-adiabatic dynamics; conical intersection; time-resolved photoelectron spectra; ionization potential; ensemble DFT
Issue or Number:8
PubMed Central ID:PMC8074317
Record Number:CaltechAUTHORS:20210503-155515372
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210503-155515372
Official Citation:Filatov M, Lee S, Nakata H, Choi C-H. Signatures of Conical Intersection Dynamics in the Time-Resolved Photoelectron Spectrum of Furan: Theoretical Modeling with an Ensemble Density Functional Theory Method. International Journal of Molecular Sciences. 2021; 22(8):4276. https://doi.org/10.3390/ijms22084276
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108950
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:04 May 2021 14:27
Last Modified:04 May 2021 14:27

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