ArticleACS physical chemistry Au2026
Ionization-Induced Electronic and Vibronic Structure of 3,5-Difluoropyridine Probed by VUV-MATI Spectroscopy.
Article in ACS physical chemistry Au, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Fluorinated pyridines, particularly difluoropyridines, exhibit position-dependent electronic properties arising from the interplay of inductive, resonance, and hyperconjugative effects introduced by fluorine substitution. In this study, the ionization-induced electronic and structural characteristics of 3,5-difluoropyridine (3,5-DFP)a previously uncharacterized meta-meta disubstituted isomerwere investigated using high-resolution vacuum ultraviolet mass-analyzed threshold ionization spectroscopy in conjunction with quantum-chemical calculations. The adiabatic ionization energy was determined to be 9.6829 ± 0.0004 eV, indicating an intermediate degree of electronic stabilization between the 2,3- and 2,5-isomers. Natural bond orbital analysis showed that the π-type HOMO of 3,5-DFP experiences moderate delocalization over the aromatic framework, whereas the σ-type HOMO-1 exhibits minimal interaction with the fluorine substituents, resulting in reduced stabilization. Franck-Condon analysis and vibrational spectroscopy revealed distinct ionization-driven geometric distortions dominated by ring-bending and stretching modes. The small D
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