Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by infrared (IR) action spectroscopy under jet-cooled conditions with selective detection of hydroxyl (OH) radical products. Two distinct •QOOH isomers with radical sites at a primary carbon of one of the methyl groups (β-Me) or a secondary carbon (β-Et) of the ethyl group are identified by comparison with theoretically calculated IR absorption features for multiple conformers, including C–O, ethyl, and O–O torsions of the two isomers. A master-equation analysis is developed and utilized to explore the conformational cooling process and the resultant conformer population distributions of the two isomers. Most of the IR features observed, including those in the strong fundamental and first overtone OH stretch regions as well as weaker combination bands involving OH stretch with torsion or OOH bend, are in good accord with computed anharmonic frequencies for the most populated conformers of the •QOOHEt isomer. Relatively weak IR features most evident in the fundamental and first overtone OH stretch regions are ascribed to multiple conformers of the less stable •QOOHMe isomer, along with a weak feature that is uniquely attributed to a combination band involving asymmetric CH2 stretch and HCH bend of •QOOHMe. The time- and energy-resolved unimolecular dynamics of the •QOOHEt and •QOOHMe isomers to OH radical products are reported in Paper II Qian et al. , J. Chem. Phys. 164, 244312 (2026).
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