Journal of Physical Chemistry, Vol.99, No.16, 5772-5786, 1995
Ultrafast Measurements of Chemistry in Clusters - Excited-State Proton-Transfer
In this article we report on the progress being made in understanding solvent interactions at the molecular level from time-resolved studies of chemistry in clusters. We begin by reviewing the variety of reactions studied in clusters by time-domain techniques. We then focus our discussion on the prototype hydrogen-bonded system ROH . B-n, where ROH is an aromatic alcohol such as phenol or naphthol and B-n is a cluster of solvent molecules. This system undergoes excited-state proton transfer and is important because it is being investigated on many fronts, e.g., dynamical, spectroscopic, and structural determinations, in clusters, and in condensed phase, along with supporting theoretical work. We review results that show a strong dependence of reaction rate on solvent type, size, and structure, in pure and binary solvents. Solvent dynamics such as structural reorganization following proton transfer are also evident. These properties, along with deuteration experiments, are indicating a tunneling mechanism for proton transfer. The effect of individual solvent molecules on the barrier properties and product energies is discussed and compared to condensed-phase studies. Throughout our discussion we take the opportunity to inject some speculation and opinion regarding future directions, outstanding issues, and conflicting results.
Keywords:ELECTRON-TRANSFER REACTIONS;REAL-TIME DYNAMICS;GAS-PHASE CLUSTERS;MASS-SELECTIVE MEASUREMENTS;NAPHTHOL AMMONIA COMPLEXES;PUMP PROBE PHOTOIONIZATION;HYDROGEN-BONDED COMPLEXES;TRANSFER-REACTION-RATES;IMPACT CROSS-SECTIONS;ACID-BASE CHEMISTRY