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A localized view on molecular dissociation via electron-ion partial covariance

Abstract:
Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1038/s42004-022-00656-w

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Author
ORCID:
0000-0002-8044-8969
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Role:
Author
ORCID:
0000-0002-5072-0837
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Author
ORCID:
0000-0003-1417-4151
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Author
ORCID:
0000-0001-6286-4064
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Author
ORCID:
0000-0001-8413-3588


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Grant:
EP/L005913/1
Ref R102215-101 (EP/V026690/1)


Publisher:
Springer Nature
Journal:
Communications Chemistry More from this journal
Volume:
5
Issue:
1
Article number:
42
Publication date:
2022-03-28
Acceptance date:
2022-02-21
DOI:
EISSN:
2399-3669


Language:
English
Keywords:
Pubs id:
1248916
Local pid:
pubs:1248916
Deposit date:
2022-03-30
ARK identifier:

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