We investigated the ultrafast structural dynamics of cyclobutanone following photoexcitation at λ = 200 nm using gas-phase megaelectronvolt ultrafast electron diffraction. Our investigation complements the simulation studies of the same process within this special issue. It provides information about both electronic state population and structural dynamics through well-separable inelastic and elastic electron scattering signatures. We observe the depopulation of the photoexcited S2 state of cyclobutanone with n3s Rydberg character through its inelastic electron scattering signature with a time constant of (0.29 ± 0.2) ps toward the S1 state. The S1 state population undergoes ring-opening via a Norrish Type-I reaction, likely while passing through a conical intersection with S0. The corresponding structural changes can be tracked by elastic electron scattering signatures. These changes appear with a delay of (0.14 ± 0.05) ps with respect to the initial photoexcitation, which is less than the S2 depopulation time constant. This behavior provides evidence for the ballistic nature of the ring-opening once the S1 state is reached. The resulting biradical species react further within (1.2 ± 0.2) ps via two rival fragmentation channels yielding ketene and ethylene, or propene and carbon monoxide. Our study showcases the value of both gas-phase ultrafast diffraction studies as an experimental benchmark for nonadiabatic dynamics simulation methods and the limits in the interpretation of such experimental data without comparison with such simulations.
Skip Nav Destination
Imaging the photochemistry of cyclobutanone using ultrafast electron diffraction: Experimental results
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
,
Article navigation
7 May 2025
Research Article|
May 12 2025
Imaging the photochemistry of cyclobutanone using ultrafast electron diffraction: Experimental results
Available to Purchase
Special Collection:
Prediction Challenge: Cyclobutanone Photochemistry
A. E. Green
;
A. E. Green
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Validation, Writing – original draft, Writing – review & editing)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
2
EaStCHEM School of Chemistry, University of Edinburgh
, Edinburgh EH9 3FJ, United Kingdom
3
European XFEL
, Holzkoppel 4, 22869 Schenefeld, Germany
Search for other works by this author on:
Y. Liu
;
Y. Liu
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
F. Allum
;
F. Allum
(Investigation, Writing – review & editing)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
M. Graßl
;
M. Graßl
(Investigation, Writing – review & editing)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
P. Lenzen
;
P. Lenzen
(Investigation, Writing – review & editing)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
M. N. R. Ashfold
;
M. N. R. Ashfold
(Investigation, Writing – review & editing)
5
School of Chemistry, University of Bristol
, Bristol BS8 1TS, United Kingdom
Search for other works by this author on:
S. Bhattacharyya
;
S. Bhattacharyya
(Investigation, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
X. Cheng
;
X. Cheng
(Investigation, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
M. Centurion
;
M. Centurion
(Funding acquisition, Investigation, Writing – review & editing)
6
Department of Physics and Astronomy, University of Nebraska-Lincoln
, Lincoln, Nebraska 68588, USA
Search for other works by this author on:
S. W. Crane
;
S. W. Crane
(Investigation, Writing – review & editing)
7
Department of Chemistry, Brown University
, Providence, Rhode Island 02912, USA
Search for other works by this author on:
R. Forbes
;
R. Forbes
(Investigation, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
8
Department of Chemistry, University of California
, One Shields Avenue, Davis, California 95616, USA
Search for other works by this author on:
N. A. Goff
;
N. A. Goff
(Investigation, Writing – review & editing)
7
Department of Chemistry, Brown University
, Providence, Rhode Island 02912, USA
Search for other works by this author on:
L. Huang
;
L. Huang
(Investigation, Writing – review & editing)
7
Department of Chemistry, Brown University
, Providence, Rhode Island 02912, USA
Search for other works by this author on:
B. Kaufman
;
B. Kaufman
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
M.-F. Kling
;
M.-F. Kling
(Funding acquisition, Investigation, Writing – review & editing)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
9
Applied Physics Department, Stanford University
, 348 Via Pueblo, Stanford, California 94305, USA
Search for other works by this author on:
P. L. Kramer
;
P. L. Kramer
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
H. V. S. Lam
;
H. V. S. Lam
(Investigation, Writing – review & editing)
10
Department of Physics, Kansas State University
, Manhattan, Kansas 66506, USA
Search for other works by this author on:
K. A. Larsen
;
K. A. Larsen
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
R. Lemons
;
R. Lemons
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
M.-F. Lin
;
M.-F. Lin
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
A. J. Orr-Ewing
;
A. J. Orr-Ewing
(Investigation, Writing – review & editing)
5
School of Chemistry, University of Bristol
, Bristol BS8 1TS, United Kingdom
Search for other works by this author on:
D. Rolles
;
D. Rolles
(Funding acquisition, Investigation, Writing – review & editing)
10
Department of Physics, Kansas State University
, Manhattan, Kansas 66506, USA
Search for other works by this author on:
A. Rudenko
;
A. Rudenko
(Funding acquisition, Investigation, Writing – review & editing)
10
Department of Physics, Kansas State University
, Manhattan, Kansas 66506, USA
Search for other works by this author on:
S. K. Saha
;
S. K. Saha
(Investigation, Writing – review & editing)
10
Department of Physics, Kansas State University
, Manhattan, Kansas 66506, USA
Search for other works by this author on:
J. Searles
;
J. Searles
(Investigation, Writing – review & editing)
10
Department of Physics, Kansas State University
, Manhattan, Kansas 66506, USA
Search for other works by this author on:
X. Shen
;
X. Shen
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
S. Weathersby
;
S. Weathersby
(Investigation, Methodology, Writing – review & editing)
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
Search for other works by this author on:
P. M. Weber
;
P. M. Weber
(Funding acquisition, Investigation, Writing – review & editing)
7
Department of Chemistry, Brown University
, Providence, Rhode Island 02912, USA
Search for other works by this author on:
H. Zhao
;
H. Zhao
(Investigation, Writing – review & editing)
6
Department of Physics and Astronomy, University of Nebraska-Lincoln
, Lincoln, Nebraska 68588, USA
Search for other works by this author on:
T. J. A. Wolf
T. J. A. Wolf
a)
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Project administration, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
a)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
A. E. Green
1,2,3
F. Allum
1
M. Graßl
1,4
P. Lenzen
1
M. N. R. Ashfold
5
S. Bhattacharyya
4
X. Cheng
4
M. Centurion
6
S. W. Crane
7
R. Forbes
4,8
N. A. Goff
7
L. Huang
7
B. Kaufman
4
M.-F. Kling
1,4,9
P. L. Kramer
4
H. V. S. Lam
10
K. A. Larsen
4
R. Lemons
4
M.-F. Lin
4
A. J. Orr-Ewing
5
D. Rolles
10
A. Rudenko
10
S. K. Saha
10
J. Searles
10
X. Shen
4
S. Weathersby
4
P. M. Weber
7
H. Zhao
6
T. J. A. Wolf
1,4,a)
1
Stanford PULSE Institute, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
2
EaStCHEM School of Chemistry, University of Edinburgh
, Edinburgh EH9 3FJ, United Kingdom
3
European XFEL
, Holzkoppel 4, 22869 Schenefeld, Germany
4
Linac Coherent Light Source, SLAC National Accelerator Laboratory
, 2575 Sand Hill Road, Menlo Park, California 94025, USA
5
School of Chemistry, University of Bristol
, Bristol BS8 1TS, United Kingdom
6
Department of Physics and Astronomy, University of Nebraska-Lincoln
, Lincoln, Nebraska 68588, USA
7
Department of Chemistry, Brown University
, Providence, Rhode Island 02912, USA
8
Department of Chemistry, University of California
, One Shields Avenue, Davis, California 95616, USA
9
Applied Physics Department, Stanford University
, 348 Via Pueblo, Stanford, California 94305, USA
10
Department of Physics, Kansas State University
, Manhattan, Kansas 66506, USA
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 162, 184303 (2025)
Article history
Received:
February 19 2025
Accepted:
April 10 2025
Citation
A. E. Green, Y. Liu, F. Allum, M. Graßl, P. Lenzen, M. N. R. Ashfold, S. Bhattacharyya, X. Cheng, M. Centurion, S. W. Crane, R. Forbes, N. A. Goff, L. Huang, B. Kaufman, M.-F. Kling, P. L. Kramer, H. V. S. Lam, K. A. Larsen, R. Lemons, M.-F. Lin, A. J. Orr-Ewing, D. Rolles, A. Rudenko, S. K. Saha, J. Searles, X. Shen, S. Weathersby, P. M. Weber, H. Zhao, T. J. A. Wolf; Imaging the photochemistry of cyclobutanone using ultrafast electron diffraction: Experimental results. J. Chem. Phys. 7 May 2025; 162 (18): 184303. https://doi.org/10.1063/5.0266559
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
GPAW: An open Python package for electronic structure calculations
Jens Jørgen Mortensen, Ask Hjorth Larsen, et al.
Related Content
Predicting the photodynamics of cyclobutanone triggered by a laser pulse at 200 nm and its MeV-UED signals—A trajectory surface hopping and XMS-CASPT2 perspective
J. Chem. Phys. (April 2024)
Ultrafast photochemistry and electron diffraction for cyclobutanone in the S2 state: Surface hopping with time-dependent density functional theory
J. Chem. Phys. (July 2024)
The photochemistry of Rydberg-excited cyclobutanone: Photoinduced processes and ground state dynamics
J. Chem. Phys. (April 2024)