Protonation sites in methyl nitrate and the formation of transient CH4NO3 radicals. A neutralization-reionization...

Protonation sites in methyl nitrate (1) were evaluated computationally at the Gaussian 2(MP2) level of ab initio theory. The methoxy oxygen was the most basic site that had a calculated proton affinity of PA = 728-738 kJ mol-1 depending on the optimization method used to calculate the equilibrium geometry of the CH3O(H)-NO2+ ion (2+). Protonation at the terminal oxygen atoms in methyl nitrate was less exothermic; the calculated proton affinities were 725, 722, and 712 kJ mol-1 for the formation of the syn-syn, anti-syn, and syn-anti ion rotamers 3a+, 3b+, and 3c+, respectively. Ion 2+ was prepared by an ion-molecule reaction of NO2+ with methanol and used to generate the transient CH3O(H)-NO2. radical (2) by femtosecond collisional electron transfer. Exothermic protonation of 1 produced a mixture of 3a(+)-3c+ with 2+ that was used to generate transient radicals 3a-3c. Radical 2 was found to be unbound and dissociated without barrier to methanol and NO2. Radicals 3a-3c were calculated to be weakly bound. When formed by vertical neutralization, 3a-3c dissociated completely on the 4.2 microseconds time scale of the experiment. The main dissociations of 3a-3c were formations of CH3O. + HONO and CH3ONO + OH.. The gas-phase chemistry of radicals 3a-3c and their dissociation products, as studied by neutralization-reionization mass spectrometry, was dominated by Franck-Condon effects on collisional neutralization and reionization. The adiabatic ionization energies of 3a-3c were calculated as 7.54, 7.57, and 7.66 eV, respectively.