EXACT AND CONSTRAINED KINETIC ENERGY OPERATORS IN POLYSPHERICAL COORDINATES

Abstract

In this paper the derivation of exact and constrained kinetic energy operators in curvilinear coordinates is presented in a very general context. The polyspherical approach allows us to provide simple and explicit expressions of these operators which are well adapted to the numerical approaches used to solve the Schrödinger equation. These expressions can be exploited to treat a lot of problems such as the calculation of infrared or photoabsorption spectra as well as the study of intramolecular vibrational relaxation of molecules or the study of reactive scattering systems. Special emphasis is placed on concrete applications.