Molecular-physics aspects of cold chemistry

Abstract

Molecular-physics aspects of cold chemistry are introduced with the example of few-electron molecules. After a brief overview of general aspects of molecular physics, the solution of the molecular Schrödinger equation is presented based on the Born-Oppenheimer approximation and the subsequent evaluation of adiabatic, nonadiabatic, relativistic and radiative (QED) corrections. Low-temperature chemical phenomena are introduced with the example of ion-molecule reactions, using the classical Langevin model for barrier-free exothermic reactions as reference. Then, methods to generate cold few-electron molecules by supersonic-beam-deceleration methods such as Stark, Zeeman, and Rydberg-Stark decelerations are presented. Two astrophysically important reactions, the reaction between H2 and H2+ forming H3+ and H, a very fast reaction following Langevin-capture going over to quantum-Langevin capture at low temperature, and the radiative association reaction H+ + H forming H2+, a very slow reaction in which quantum effects (shape resonances) become important at low temperatures, are used to illustrate the concepts introduced.