RT info:eu-repo/semantics/article
T1 Fragmentation dynamics of benzoyl peroxide: Insights from rotational spectroscopy
A1 Mato Domínguez, Sergio
A1 Municio, Sofía
A1 Alonso Hernández, José Luis
A1 Alonso Alonso, Elena Rita
A1 León Ona, Iker
K1 Ablation
K1 Degradation
K1 Organic reactions
K1 Oxides
K1 Spectroscopy
K1 2210 Química Física
AB Benzoyl peroxide (BPO) represents a structurally simple yet hazardous organic peroxide with widespread applications across industrial and pharmaceutical domains. Despite its extensive use, detailed molecular-level understanding of its thermal instability remains limited. Here, we present the first rotational spectroscopy characterization of isolated BPO in the gas phase, enabled by laser ablation and supersonic jet expansion techniques. Our analysis reveals a C2-symmetric structure with quasi-perpendicular aromatic rings, in excellent agreement with crystallographic data. Quantum chemical calculations and topological analysis identify a stabilizing reciprocal n→π* interaction between adjacent carbonyl groups that may contribute to BPO’s thermal resilience compared to other organic peroxides. Furthermore, we detect several photofragmentation products, including benzoic acid, benzyne, benzaldehyde, and benzophenone, providing insights into potential decomposition pathways. This molecular-level investigation bridges the gap between macroscopic hazard assessments and fundamental understanding of peroxide reactivity, with implications for safer handling and rational design of peroxide-based systems.
PB American Chemical Society
SN 1948-7185
YR 2025
FD 2025
LK https://uvadoc.uva.es/handle/10324/79564
UL https://uvadoc.uva.es/handle/10324/79564
LA eng
NO The Journal of Physical Chemistry Letters, 2025, vol. 16, n. 44, p. 11597-11603
NO Producción Científica
DS UVaDOC
RD 04-dic-2025