Large ammonia clusters represent a model system of ices that are omnipresent throughout the space. The interaction of ammonia ices with other hydrogen-boding molecules such as methanol or water and their behavior upon an ionization are thus relevant in the astrochemical context. In this study, ammonia clusters (NH₃) _N with the mean size N̅ ≈ 230 were prepared in molecular beams and passed through a pickup cell in which methanol molecules were adsorbed. At the highest exploited pickup pressures, the average composition of (NH₃) _N(CH₃OH) _M clusters was estimated to be N: M ≈ 210:10. On the other hand, the electron ionization of these clusters yielded about 75% of methanol-containing fragments (NH₃) _n(CH₃OH) _mH⁺ compared to 25% contribution of pure ammonia (NH₃) _nH⁺ ions. On the basis of this substantial disproportion, we propose the following ionization mechanism: The prevailing ammonia is ionized in most cases, resulting in NH₄⁺ core solvated most likely with four ammonia molecules, yielding the well-known "magic number" structure (NH₃)₄NH₄⁺. The methanol molecules exhibit a strong propensity for sticking to the fragment ion. We have also considered mechanisms of intracluster reactions. In most cases, proton transfer between ammonia units take place. The theoretical calculations suggested the proton transfer either from the methyl group or from the hydroxyl group of the ionized methanol molecule to ammonia to be the energetically open channels. However, the experiments with selectively deuterated methanols did not show any evidence for the D⁺ transfer from the CD₃ group. The proton transfer from the hydroxyl group could not be excluded entirely or confirmed unambiguously by the experiment.

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