Ultrafast Proton-Transfer Reaction in Phenol-(Ammonia)n Clusters: An Ab Initio Molecular Dynamics Investigation.

Abstract

The ability of phenol to transfer a proton to surrounding ammonia molecules in a phenol-(ammonia)n cluster depends on the relative orientation of ammonia molecules, and a critical field of about 285 MV cm-1 is essential along the O-H bond for the proton-transfer process. Ab initio MD simulations reveal that the proton-transfer process from phenol to ammonia cluster is spontaneous when the cluster has at least eight ammonia molecules, and the proton-transfer event is almost instantaneous (about 20-120 fs). These simulations also reveal that the rate-determining step for the proton-transfer process is the reorganization of the solvent around the OH group. During the solvent reorganization process, the fluctuations in the solvent occur until a particular set of configurations projects the field in excess of the critical electric field along the O-H bond which drives the proton-transfer process. Further, the proton-transfer process follows a curvilinear path which includes the O-H bond elongation and out-of-plane movement of the proton and can be referred to as a "bend-to-break" process.