A theoretical study on the size-dependence of ground-state proton transfer in phenol–ammonia clusters

Abstract

Geometries and infrared (IR) spectra in the mid-IR region of phenol–(ammonia)_n (PhOH–(NH₃)_n) (n = 0–10) clusters have been studied using density functional theory (DFT) to investigate the critical number of solvent molecules necessary to promote ground-state proton transfer (GSPT). For n ≤ 8 clusters, the most stable isomer is a non-proton-transferred (non-PT) structure, and all isomers found within 1.5 kcal mol⁻¹ from it are also non-PT structures. For n = 9, the most stable isomer is also a non-PT structure; however, the second stable isomer is a PT structure, whose relative energy is within the experimental criterion of population (0.7 kcal mol⁻¹). For n = 10, the PT structure is the most stable one. We can therefore estimate that the critical size of GSPT is n = 9. This is confirmed by the fact that these calculated IR spectra are in good accordance with our previous experimental results of mid-IR spectra. It is demonstrated that characteristic changes of the ν_9a and ν₁₂ bands in the skeletal vibrational region provide clear information that the GSPT reaction has occurred. It was also found that the shortest distance between the π-ring and the solvent moiety is a good indicator of the PT reaction.