Dynamics of Ion-Molecule Complexes

William L Hase

Jul 2016 · Elsevier

About this ebook

Advances in Classical Trajectory Methods, Volume 2: Dynamics of Ion-Molecule Complexes is a seven-chapter text that covers the considerable advances in the experimental and theoretical aspects of ion-molecular complexes, with particular emphasis on the dynamics and kinetics of their formation and ensuing unimolecular dissociation. This text also considers the development and testing of theoretical models for these formation and decomposition processes. The opening chapters discuss photoelectron photoion coincidence, ion cyclotron resonance, and crossed molecular beam studies of metastable ion-molecule complexes formed in ion-molecule collisions. These experimental studies involve comparisons with the predictions of statistical models, such as the Rice-Ramsperger-Kassel-Marcus and phase space theories, and comparisons with the reaction dynamics predicted by classical trajectory calculations. The succeeding chapter describes the double-well model for ion-molecular reactions taking place on a potential energy surface with a central barrier that separates two potential energy minima. These topics are followed by reviews of the quantum chemical calculation and reaction path Hamiltonian analysis of SN2 reactions, the transition state theory for ion-dipole and ion-quadrupole capture, and the capture and dynamical models for ion-molecule association to form a complex. The remaining chapters consider the temperature dependence of ion-molecule reactions, which proceed on a surface with many potential energy minima, specifically the ability to establish asymptotic limits for the reaction efficiency dependent upon the number of potential minima and the above relative probabilities. This book is of great value to experimental and theoretical chemists and physicists.