We simulate the photodynamics of gas-phase cyclobutanone excited to the S2 state using fewest switches surface hopping (FSSH) dynamics powered by time-dependent density functional theory (TDDFT). We predict a total photoproduct yield of 8%, with a C3:C2 product ratio of 0 trajectories to 8 trajectories. One primary S2 → S1 conical intersection is identified involving the compression of an α-carbon–carbon–hydrogen bond angle. Excited state lifetimes computed with respect to electronic state populations were found to be 3.96 ps (S2 → S1) and 498 fs (S1 → S0). We also generate time-resolved difference pair distribution functions (ΔPDFs) from our TDDFT-FSSH dynamics results in order to generate direct comparisons with ultrafast electron diffraction experiment observables. Global and target analysis of time-resolved ΔPDFs produced a distinct set of lifetimes: (i) a 0.548 ps decay and (ii) a 1.69 ps decay, both resembling the S2 minimum, as well as (iii) a long decay that resembles the S1 minimum geometry and the fully separated C2 products. Finally, we contextualize our results by considering the impact of the most likely sources of significant errors.
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21 July 2024
Research Article|
July 15 2024
Ultrafast photochemistry and electron diffraction for cyclobutanone in the S2 state: Surface hopping with time-dependent density functional theory Available to Purchase
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Prediction Challenge: Cyclobutanone Photochemistry
Ericka Roy Miller
;
Ericka Roy Miller
(Conceptualization, Investigation, Methodology, Project administration, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Case Western Reserve University
, 10900 Euclid Ave., Cleveland, Ohio 44106, USA
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Sean J. Hoehn
;
Sean J. Hoehn
(Conceptualization, Investigation, Methodology, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Case Western Reserve University
, 10900 Euclid Ave., Cleveland, Ohio 44106, USA
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Abhijith Kumar
;
Abhijith Kumar
(Conceptualization, Investigation, Methodology, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Case Western Reserve University
, 10900 Euclid Ave., Cleveland, Ohio 44106, USA
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Dehua Jiang
;
Dehua Jiang
(Conceptualization, Investigation, Methodology, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Case Western Reserve University
, 10900 Euclid Ave., Cleveland, Ohio 44106, USA
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Shane M. Parker
Shane M. Parker
a)
(Conceptualization, Methodology, Supervision, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, Case Western Reserve University
, 10900 Euclid Ave., Cleveland, Ohio 44106, USA
a)Author to whom correspondence should be addressed: [email protected]
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Ericka Roy Miller
Sean J. Hoehn
Abhijith Kumar
Dehua Jiang
Shane M. Parker
a)
Department of Chemistry, Case Western Reserve University
, 10900 Euclid Ave., Cleveland, Ohio 44106, USA
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 034105 (2024)
Article history
Received:
February 15 2024
Accepted:
June 26 2024
Citation
Ericka Roy Miller, Sean J. Hoehn, Abhijith Kumar, Dehua Jiang, Shane M. Parker; Ultrafast photochemistry and electron diffraction for cyclobutanone in the S2 state: Surface hopping with time-dependent density functional theory. J. Chem. Phys. 21 July 2024; 161 (3): 034105. https://doi.org/10.1063/5.0203679
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