Perspective on a challenge: Predicting the photochemistry of cyclobutanone
Abstract
This Perspective is part of a Special Topic that explored the maturity of nonadiabatic molecular dynamics for predicting photochemical processes. In 2023, a prediction challenge was issued to the community of computational photochemists to simulate the photochemistry of cyclobutanone, photoexcited at 200 nm, and the resulting time-resolved mega-electronvolt ultrafast electron diffraction (MeV-UED) signal. The challenge attracted 15 theoretical predictions from more than 70 researchers, employing a wide range of strategies for electronic structure and nonadiabatic molecular dynamics to predict the time-resolved MeV-UED signal before the experiment had been conducted at SLAC (Stanford, USA). The MeV-UED instrument at Shanghai Jiao Tong University was also used to provide a second independent time-resolved MeV-UED signal for the photochemistry of cyclobutanone. This Perspective discusses the various approaches and strategies used by the participants to predict the photochemistry of cyclobutanone. This work also summarizes the strengths and weaknesses of various methods used for photoexcitation, electronic structure, nonadiabatic dynamics, and calculation of observables, as agreed by the participants during a CECAM workshop dedicated to the results of the challenge and organized in Lausanne in April 2025. This Perspective also collects all the predicted time-resolved MeV-UED signals into a single figure, together with the experimental signal. The challenge (i) demonstrated the qualitative predictive power of nonadiabatic molecular dynamics and (ii) underscored the impact of electronic-structure theory on the outcome of the excited-state dynamics and the need for its careful benchmarking. This effort allowed the community to share practical strategies to perform nonadiabatic dynamics (discussed in the present Perspective) and constitutes a “calibration” exercise for computational photochemistry.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (40)
Jiří Janoš
School of Chemistry, University of Bristol 1 , Bristol BS8 1TS,
Nanna Holmgaard List
School of Chemistry, University of Birmingham 3 , Birmingham B15 2TT,
Andrew J. Orr-Ewing
School of Chemistry
Jiří Suchan
Institute for Advanced Computational Science, Stony Brook University 5 , Stony Brook, New York 11794,
Mario Barbatti
Aix Marseille University, CNRS, ICR 1 , Marseille,
Olivia Bennett
Marcus Brady
Department of Chemistry, University College London 8 , 20 Gordon St., WC1H 0AJ London,
Javier Carmona-García
Centre for Computational Chemistry, School of Chemistry
Rachel Crespo-Otero
Department of Chemistry
Julien Eng
Chemistry – School of Natural and Environmental Sciences
O. Jonathan Fajen
Department of Chemistry and The PULSE Institute, Stanford University 10 , Stanford, California 94305,
Marco Garavelli
Dipartimento di Chimica industriale “Toso Montanari”, Università di Bologna, Via Piero Gobetti 85, Bologna 40129, Italy
Sandra Gómez
Departamento de Química, Módulo 13, Universidad Autónoma de Madrid 13 , 28049 Madrid,
Alice E. Green
EaStCHEM School of Chemistry
Federico J. Hernández
Department of Chemistry, Queen Mary University of London. Mile End Road, London. E1 4NS, U.K.
Daniel Hollas
School of Chemistry, University of Bristol 1 , Bristol BS8 1TS,
Lewis Hutton
Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford 16 , Oxford OX1 3QZ,
Lea M. Ibele
Aix Marseille University, CNRS, ICR
Adam Kirrander
Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford 16 , Oxford OX1 3QZ,
Zhenggang Lan
MOE Key Laboratory of Environmental Theoretical Chemistry, SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety, School of Environment, South China Normal University 3 , Guangzhou 510006,
Yorick Lassmann
School of Chemistry, University of Bristol 1 , Bristol BS8 1TS,
Joseph E. Lawrence
Simons Center for Computational Physical Chemistry, New York University 18 , New York, New York 10003,
Benjamin G. Levine
Department of Chemistry
Dmitry V. Makhov
School of Chemistry, University of Leeds 21 , Leeds LS2 9JT,
Jonathan R. Mannouch
The Max Planck Institute for the Structure and Dynamics of Matter 4 , 22761 Hamburg,
Xincheng Miao
Institut für Physikalische und Theoretische Chemie, Julius-Maximilians-Universität Würzburg 23 , Emil-Fischer-Straße 42, 97074 Würzburg,
Roland Mitric
Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer Str. 42, 97074 Würzburg, Germany
Shane M. Parker
Department of Chemistry, Case Western Reserve University 24 , Cleveland, Ohio 44106,
Thomas J. Penfold
Chemistry – School of Natural and Environmental Sciences
Jiawei Peng
SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental Theoretical Chemistry, School of Environment, South China Normal University 17 , Guangzhou 510006,
Jeremy O. Richardson
Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 3, Zurich CH-8093, Switzerland
Dmitrii Shalashilin
School of Chemistry, University of Leeds 21 , Leeds LS2 9JT,
Petr Slavíček
Department of Physical Chemistry, University of Chemistry and Technology 7 , Technická 5, Prague 6 166 28,
K. Eryn Spinlove
Department of Chemistry, University College London 8 , 20 Gordon St., WC1H 0AJ London,
Patricia Vindel-Zandbergen
Department of Chemistry, New York University 19 , New York, New York 10003,
Federica Agostini
Sara Bonella
Centre Européen de Calcul Atomique et Moléculaire
Todd J. Martinez
Department of Chemistry
Graham A. Worth
Department of Chemistry, University College London 9 , 20 Gordon St., London WC1H 0AJ,
Basile F. E. Curchod
School of Chemistry, Cantock’s Close