Adamantane, the smallest diamondoid molecule with a symmetrical cage, contains two distinct carbon sites, CH and CH2. The ionization/excitation of the molecule leads to the cage opening and strong structural reorganization. While theoretical predictions suggest that the carbon site CH primarily causes the cage opening, the role of the other CH2 site remains unclear. In this study, we used advanced experimental Auger electron-ion coincidence techniques and theoretical calculations to investigate the fragmentation dynamics of adamantane after resonant inner-shell photoexcitation. Our results demonstrate that some fragmentation channels exhibit site-sensitivity of the initial core-hole location, indicating that different carbon site excitations could lead to unique cage opening mechanisms.

Condensed Matter Physics Center Universidad Autónoma de Madrid 28049 Madrid Spain

Department of Chemistry Universidad Autonoma de Madrid 28049 Madrid Spain

Department of Physical Chemistry University of Chemistry and Technology Technická 5 166 28 Prague Czech Republic

Department of Physics Lund University 22100 Lund Sweden

Department of Physics University of Gothenburg Origovagen 6 B 41296 Gothenburg Sweden

Institut Lumiere Matiere UMR 5306 Universite Claude Bernard Lyon 1 CNRS Univ Lyon 69100 Villeurbanne France

Institute for Advanced Research in Chemistry Universidad Autónoma de Madrid 28049 Madrid Spain

Normandie University ENSICAEN UNICAEN CEA CNRS CIMAP 14000 Caen France

Synchrotron SOLEIL L'Orme de Merisiers Saint Aubin BP48 91192 Gif sur Yvette CEDEX France

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