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Peer-reviewedCC BYThe journal of physical chemistry. A

Microsolvation Controls Ultrafast Relaxation Pathways in Hydrated Pyridine.

  • Deepthy Maria Mootheril1
  • Anna D Skitnevskaya2
  • Xueguang Ren3
  • Alexander I Kuleff4
  • Alexander B Trofimov2
  • Lorenz S Cederbaum4
  • Thomas Pfeifer1
  • Alexander Dorn1
4 affiliations
  1. 1Max-Planck-Institut Für Kernphysik , Saupfercheckweg 1, 69117Heidelberg, Germany.
  2. 2Federal Research Center, A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 664033Irkutsk, Russia.
  3. 3MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi'an Jiaotong University, Xi'an710049, China.
  4. 4Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, 69120Heidelberg, Germany.
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Abstract

Hydration critically reshapes ultrafast electronic relaxation in biorelevant molecules, yet its mechanistic role remains poorly understood. Here, we investigate intermolecular Coulombic decay (ICD) following medium-energy (E0 = 103 eV) electron impact ionization of hydrated pyridine, a prototypical nucleobase analogue. Combining multiparticle momentum coincidence spectroscopy with high-level electronic structure calculations, we identify water-initiated ICD and find evidence consistent with an additional pyridine-initiated ICD pathway, in which inner-valence ionization leads to ionization of the neighboring molecule. Water vacancies decay exclusively via the ICD, establishing a highly efficient direct channel. In contrast, pyridine vacancies compete with Auger decay, reducing the efficiency of the pyridine-to-water ICD pathway. As in pyridine dimers, heterocycle-initiated ICD is dominated by N 2s vacancy states. Our results reveal a dual role of water: it opens a highly efficient direct ICD pathway via O 2s vacancy states and acts as an energy-accepting partner following biomolecular inner-valence ionization. These results reveal how microsolvation governs ultrafast relaxation and shapes radiation-induced damage pathways in DNA-related systems.

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Cite

BibTeXRIS
BibTeX
@article{mootheril2026microsolvation,
  title = {{Microsolvation Controls Ultrafast Relaxation Pathways in Hydrated Pyridine.}},
  author = {Deepthy Maria Mootheril and Anna D Skitnevskaya and Xueguang Ren and Alexander I Kuleff and Alexander B Trofimov and Lorenz S Cederbaum and Thomas Pfeifer and Alexander Dorn},
  journal = {The journal of physical chemistry. A},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.jpca.6c05980},
  url = {https://europepmc.org/article/MED/42911004},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Microsolvation Controls Ultrafast Relaxation Pathways in Hydrated Pyridine.
AU  - Deepthy Maria Mootheril
AU  - Anna D Skitnevskaya
AU  - Xueguang Ren
AU  - Alexander I Kuleff
AU  - Alexander B Trofimov
AU  - Lorenz S Cederbaum
AU  - Thomas Pfeifer
AU  - Alexander Dorn
PY  - 2026
DA  - 2026/10/01
JO  - The journal of physical chemistry. A
DO  - 10.1021/acs.jpca.6c05980
UR  - https://europepmc.org/article/MED/42911004
AB  - Hydration critically reshapes ultrafast electronic relaxation in biorelevant molecules, yet its mechanistic role remains poorly understood. Here, we investigate intermolecular Coulombic decay (ICD) following medium-energy (E0 = 103 eV) electron impact ionization of hydrated pyridine, a prototypical nucleobase analogue. Combining multiparticle momentum coincidence spectroscopy with high-level electronic structure calculations, we identify water-initiated ICD and find evidence consistent with an additional pyridine-initiated ICD pathway, in which inner-valence ionization leads to ionization of the neighboring molecule. Water vacancies decay exclusively via the ICD, establishing a highly efficient direct channel. In contrast, pyridine vacancies compete with Auger decay, reducing the efficiency of the pyridine-to-water ICD pathway. As in pyridine dimers, heterocycle-initiated ICD is dominated by N 2s vacancy states. Our results reveal a dual role of water: it opens a highly efficient direct ICD pathway via O 2s vacancy states and acts as an energy-accepting partner following biomolecular inner-valence ionization. These results reveal how microsolvation governs ultrafast relaxation and shapes radiation-induced damage pathways in DNA-related systems.
SN  - 1089-5639
SN  - 1520-5215
ER  -