Methyl formate, HCOOCH3, is a well-known interstellar molecule prominent in the spectra of hot molecular cores. The current view of its formation is that it occurs in the gas phase from precursor methanol, which is synthesized on the surfaces of grain mantles during a previous colder era and evaporates while temperatures increase during the process of high-mass star formation. The specific reaction sequence thought to form methyl formate, the ion-molecule reaction between protonated methanol and formaldehyde followed by dissociative recombination of the protonated ion (HCO(H)OCH3)+, has not been studied in detail in the laboratory. We present here the results of both a quantum chemical study of the ion-molecule reaction between (CH3OH2)+ and H2CO as well as new experimental work on the system. In addition, we report theoretical and experimental studies for a variety of other possible gas-phase reactions leading to ion precursors of methyl formate. The studied chemical processes leading to methyl formate are included in a chemical model of hot cores. Our results show that none of these gas-phase processes produces enough methyl formate to explain its observed abundance. Subject headinggs: ISM: molecules — molecular data — molecular processes — radio lines: ISM

The infrared multiphoton dissociation (IRMPD) spectra of three homogenous proton-bound dimers are presented and the major features are assigned based on comparisons with the neutral alcohol and with density functional theory calculations. As well, the IRMPD spectra of protonated propanol and the propanol/water proton-bound dimer (or singly hydrated protonated propanol) are presented and analysed. Two primary IRMPD photoproducts were observed for each of the alcohol proton bound dimers and were found to vary with the frequency of the radiation impinging upon the ions. For example, when the proton-bound dimer absorbs weakly a larger amount of S_N2 product, protonated ether and water, are observed. When the proton-bound dimer absorbs more strongly, an increase in the simple dissociation product, protonated alcohol and neutral alcohol, is observed. With the aid of RRKM calculations this frequency dependence of the branching ratio is explained by assuming that photon absorption is faster than dissociation for these species and that only a few photons extra are necessary to make the higher-energy dissociation channel (simple cleavage) competitive with the lower energy (S_N2) reaction channel.

Infrared multiphoton dissociation spectra of three homogeneous and two heterogeneous proton-bound dimers were recorded in the gas phase. Comparison of the experimental infrared spectra recorded in the fingerprint region of the proton-bound dimers with spectra predicted by electronic structure calculations shows that all modes which are observed contain motion of the proton oscillating between the two monomers. The O–H–O asymmetric stretch for the homogeneous dimers is shown to occur at around 800 cm⁻¹. As expected, the O–H–O asymmetric stretching modes for the heterogeneous proton-bound dimers are observed to shift to significantly higher energy with respect to those for the homogeneous proton-bound dimers due to the asymmetry of the O–H–O moeity. This shift is shown to be predictable from the difference in proton affinities between the two monomers. Density functional predictions of the infrared spectra based on the harmonic oscillator model are demonstrated to predict the observed spectra of the homogeneous proton-bound dimers with reasonable accuracy. Calculations of the structure and infrared spectrum of protonated diglyme at the B3LYP/6-31+G** level and basis also agree well with an infrared spectrum recorded previously. For both heterogeneous proton-bound dimers, however, the predicted spectra are blue-shifted with respect to experiment.

Matrices formed by subjecting methanol vapor diluted in argon/krypton mixtures to electron bombardment and subsequent matrix isolation (EBMI) reveal a new feature at 885.3 cm−1 which is assigned to the v3 fundamental of the triatomic cation (ArHKr)+. In samples containing about 5% krypton, the v3 fundamental of Kr2H+ is also observed in a predominantly solid argon environment. These assignments are supported by annealing experiments and by density functional theory calculations reported in a separate paper. Similar experiments with xenon diluted in argon yield infrared spectra showing the v3 and v3+v1 bands of (ArHXe)+, and v3 of Xe2H+ in predominantly argon environments. EBMI of methanol diluted in krypton in the presence of xenon gives rise to infrared bands assigned to the v3 and v3+v1 fundamentals and combination bands of both (KrHXe)+ and Xe2H+ isolated in predominantly krypton environments. The energetics and plausible mechanisms to the formation of these homogenous and mixed proton-bound rare-gas dimers are considered.