Photoionization of Two Potential Biofuel Additives: γ-Valerolactone and Methyl Butyrate

The photoionization of two potential biofuel additives, γ-valerolactone (GVL, C₅H₈O₂) and methyl butyrate (MB, C₅H₁₀O₂) has been studied by imaging photoelectron photoion coincidence spectroscopy (iPEPICO) at the VUV beamline of the Swiss Light Source (SLS). The vibrational fine structure in the photoelectron spectrum is compared with a Franck-Condon simulation for the electronic ground-state band of the GVL cation. In the lowest energy dissociative photoionization channel of GVL, CO₂ is lost, resulting in a 1-butene fragment ion with a 0 K appearance energy of E₀ = 10.35 ± 0.01 eV. A newly calculated 1-butene ionization energy of 9.595 ± 0.015 eV establishes the reverse barrier height to CO₂ loss as 66.6 ± 4.3 kJ mol^-1. Methyl butyrate cations undergo McLafferty rearrangement, which explains the missing ion signal at the computed adiabatic ionization energy of 9.25 eV. After H transfer, ethylene is lost in the lowest energy dissociation channel to yield the methyl acetate enol ion at E₀ = 10.24 ± 0.04 eV. This value connects the energetics of methyl butyrate with that of methyl acetate enol ion, which is established at Δ_fH^o_0K[CH₂C(OH)OCH₃⁺] = 502 ± 6 kJ mol^-1. Parallel to ethylene loss, methyl loss is also observed from the enol tautomer of the parent ion. Both samples exhibit low-energy nonstatistical dissociative ionization channels. In GVL, the methyl-loss abundance rises quickly but levels off suddenly in the energy range of the first electronically excited states, indicating nonstatistical competition between CH₃ and CO₂ loss. In MB, the major parallel dissociation channel is the loss of a methoxy radical. Calculations indicate that McLafferty rearrangement is inhibited on the excited-state surface. Indeed, breakdown curve modeling of this and a sequential CO-loss channel confirms a second statistical regime in dissociative photoionization, decoupled from ethylene loss.