Revisiting Kassman’s path deletion procedure for the eigenvector coefficients of molecular graphs

Abstract

Kassman’s path deletion procedure for the determination of eigenvector polynomials (EPs) and hence the eigenvector or molecular orbital (MO) coefficients of a molecular graph is revisited with required proofs and illustrations. As EPs vanish for n-fold degenerate eigenvalues, the calculation of eigenvector (MO) coefficients for such an eigenvalue requires (n-1)-th derivative of each EP. The eigenvector coefficients for other degenerate eigenvalues are then obtained by exploiting the inherent symmetry of the molecular graph. The method of symmetry-factorisation followed by the path deletion procedure makes such calculations straightforward and simple as symmetry-factorisation distributes the degenerate eigenvalues (if there are any) in the fragmented graphs and the problem of degeneracy is thus avoided in calculating the MO coefficients for the individual fragments. The procedure is illustrated with the molecular graphs having non-degenerate and degenerate eigenvalues.