Second moments and rotational spectroscopy

Abstract

Although determining molecular structure using microwave spectroscopy is a mature technique, there are still simple but powerful insights to analysis of the data which are not generally appreciated. This paper summarizes three applications of second (or planar) moments which quickly and easily provide insights and conclusions about a molecule’s structure not easily obtained from the molecule’s rotational constants.If the molecule has a plane of symmetry, group second moments can verify that property and determine which groups are located on that plane. Common groups contribute predictable values to second moments. This study examines the contribution and transferability of CH2/CH3, CF2/CF3, isopropyl, and phenyl groups to molecular constants.Structures of related molecules can be critically compared using their second moments.A third application to any molecule, even those whose structures have only the identity symmetry element, determines bond lengths and angles which exactly reproduce experimentally determined 2nd moments, rotational constants, and moments of inertia. Approximate least squares methods are not needed.