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Raman and infrared spectra of isopropyl nitrate and isobutyl nitrate are reported. These spectra are used in combination with computational studies employing density functional theory at the B3-LYP/6-31G* level to assign the vibrational transitions to their corresponding normal coordinates. Similar to other alkyl nitrates, the frequency of the NO2 symmetric stretch remains relatively unchanged while the asymmetric stretch shifts to lower frequency with increasing α-carbon substitution. The mode assignments involving the photochemically relevant &z.sbnd;ONO2 chromophore agree well with those from previous infrared work. Raman depolarization ratios are also presented, and provide evidence that the condensed phase, ground-state molecular structure of isobutyl nitrate is of Cs symmetry. In contrast, the minimum energy structure of isopropyl nitrate is predicted to contain a pronounced twist around the C&z.sbnd;O bond relative to the Cs-symmetry structure that lies 2.6 kcal/mol higher in energy. Infrared intensities of isopropyl nitrate are consistent with the twisted geometry, demonstrating that this conformer is favored in solution. [Copyright &y& Elsevier]