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Structural or population dynamics: what is revealed by the time-resolved photoelectron spectroscopy of 1,3-cyclohexadiene? A study with an ensemble density functional theory method

Filatov, Michael and Lee, Seunghoon and Nakata, Hiroya and Choi, Cheol Ho (2020) Structural or population dynamics: what is revealed by the time-resolved photoelectron spectroscopy of 1,3-cyclohexadiene? A study with an ensemble density functional theory method. Physical Chemistry Chemical Physics, 22 (31). pp. 17567-17573. ISSN 1463-9076. https://resolver.caltech.edu/CaltechAUTHORS:20200728-090350281

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Abstract

Time-resolved photoelectron spectra during the photochemical ring-opening reaction of 1,3-cyclohexadiene (CHD) are modeled by an ensemble density functional theory (eDFT) method. The computational methodology employed in this work is capable of correctly describing the multi-reference effects arising in the ground and excited electronic states of molecules, which is important for the correct description of the ring-opening reaction of CHD. The geometries of molecular species along the non-adiabatic molecular dynamics (NAMD) trajectories reported in a previous study of the CHD photochemical ring-opening were used in this work to calculate the ionization energies and the respective Dyson orbitals for all possible ionization channels. The obtained theoretical time-resolved spectra display decay characteristics in a reasonable agreement with the experimental observations; i.e., the decay (and rise) of the most mechanistically significant signals occurs on the timescale of 100–150 fs. This is very different from the excited state population decay characteristics (τ _(S1) = 234 ± 8 fs) obtained in the previous NAMD study. The difference between the population decay and the decay of the photoelectron signal intensity is traced back to the geometric transformation that the molecule undergoes during the photoreaction. This demonstrates the importance of including the geometric information in interpretation of the experimental observations.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/d0cp02963gDOIArticle
http://www.rsc.org/suppdata/d0/cp/d0cp02963g/d0cp02963g1.pdfPublisherSupplementary Information
ORCID:
AuthorORCID
Filatov, Michael0000-0002-1541-739X
Choi, Cheol Ho0000-0002-8757-1396
Additional Information:© 2020 the Owner Societies. Submitted 02 Jun 2020; Accepted 15 Jul 2020; First published 20 Jul 2020. This work was supported by the National Research Foundation of Korea (NRF) grant 2019H1D3A2A02102948. No conflict of interest is declared.
Funders:
Funding AgencyGrant Number
National Research Foundation of Korea2019H1D3A2A02102948
Issue or Number:31
Record Number:CaltechAUTHORS:20200728-090350281
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200728-090350281
Official Citation:Structural or population dynamics: what is revealed by the time-resolved photoelectron spectroscopy of 1,3-cyclohexadiene? A study with an ensemble density functional theory method. Phys. Chem. Chem. Phys., 2020, 22, 17567-17573; doi: 10.1039/d0cp02963g
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:104599
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:28 Jul 2020 20:04
Last Modified:20 Aug 2020 17:52

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