Paper detail

A Fast Algorithm for the Construction of Integrity Bases Associated to Symmetry-Adapted Polynomial Representations. Application to Tetrahedral XY4 Molecules

Invariant theory provides more efficient tools, such as Molien generating functions and integrity bases, than basic group theory, that relies on projector techniques for the construction of symmetry--adapted polynomials in the symmetry coordinates of a molecular system, because it is based on a finer description of the mathematical structure of the latter. The present article extends its use to the construction of polynomial bases which span possibly, non--totally symmetric irreducible representations of a molecular symmetry group. Electric or magnetic observables can carry such irreducible representations, a common example is given by the electric dipole moment surface. The elementary generating functions and their corresponding integrity bases, where both the initial and the final representations are irreducible, are the building blocks of the algorithm presented in this article, which is faster than algorithms based on projection operators only. The generating functions for the full initial representation of interest are built recursively from the elementary generating functions. Integrity bases which can be used to generate in the most economical way symmetry--adapted polynomial bases are constructed alongside in the same fashion. The method is illustrated in detail on XY4 type of molecules. Explicit integrity bases for all five possible final irreducible representations of the tetrahedral group have been calculated and are given in the supplemental material associated with this paper.