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X-ray induced Coulomb explosion imaging of transient excited-state structural rearrangements in CS2

Abstract:
Structural imaging of transient excited-state species is a key goal of molecular physics, promising to unveil rich information about the dynamics underpinning photochemical transformations. However, separating the electronic and nuclear contributions to the spectroscopic observables is challenging, and typically requires the application of high-level theory. Here, we employ site-selective ionisation via ultrashort soft X-ray pulses and time-resolved Coulomb explosion imaging to interrogate structural dynamics of the ultraviolet photochemistry of carbon disulfide. This prototypical system exhibits the complex motifs of polyatomic photochemistry, including strong non-adiabatic couplings, vibrational mode couplings, and intersystem crossing. Immediately following photoexcitation, we observe Coulomb explosion signatures of highly bent and stretched excited-state geometries involved in the photodissociation. Aided by a model to interpret such changes, we build a comprehensive picture of the photoinduced nuclear dynamics that follows initial bending and stretching motions, as the reaction proceeds towards photodissociation.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1038/s42005-023-01414-7

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
ORCID:
0000-0001-6009-6735
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
ORCID:
0000-0002-8044-8969
More by this author
Role:
Author
ORCID:
0000-0001-5873-0290


Publisher:
Springer Nature
Journal:
Communications Physics More from this journal
Volume:
6
Issue:
1
Article number:
309
Publication date:
2023-10-20
Acceptance date:
2023-10-04
DOI:
EISSN:
2399-3650


Language:
English
Keywords:
Pubs id:
1556010
Local pid:
pubs:1556010
Deposit date:
2023-11-01
ARK identifier:

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