Quantenchemische Rechnungen an Stickstoffbasen. Teil 4*: Zur Berechnung der Polarisierbarkeiten aliphatischer Amine mit der MINDO /3-FP-Methode

Abstract

The polarizabilities of some primary, secondary, and tertiary amines have been calculated with the MINDO/3-FP-method. The calculated values are found to correlate with the experimental polarizabilities and with those determined by the method of Miller and Savchik in a satisfying manner. In addition atomic polarizabilities have been calculated according to the method of Metzger. Averaging over the calculated mean atomic polarizabilities of hydrogen, carbon, and nitrogen yields increments which, when used to recalculate molecular polarizabilities, lead to values which correlate in an excellent manner with those determined from densities and refraction indices by means of the Lorenz-Lorentz-equation. Because different nitrogen increments have been determined for primary, secondary and tertiary amines, the parameters presented here make it possible to distinguish between constitutional isomers as long as they belong to different groups (i.e. primary, secondary, and tertiary amines), something which cannot be done using the method of Miller and Savchik. The increments derived do not only allow to predict the polarizabilities of primary, secondary and tertiary amines but can be used to calculate the corresponding values for hydrazines and polyfunctional amines with equal success.