Journal of Chemical Physics, Vol.110, No.6, 2785-2799, 1999
Density- and density-matrix-based coupled Kohn-Sham methods for dynamic polarizabilities and excitation energies of molecules
Basis set methods for calculating dynamic polarizabilities and excitation energies via coupled Kohn-Sham equations within time-dependent density functional theory are introduced. The methods can be employed after solving the ground state Kohn-Sham equations with a fitting function approach. Successful applications of the methods to test molecules are presented. Coupled Kohn-Sham methods based on the linear response of the Kohn-Sham density matrix are derived from the standard coupled Kohn-Sham equation based on the linear response of the electron density and the relations between the two types of coupled Kohn-Sham equations are investigated. The choice of norm functions associated with basis set representations of the coupled Kohn-Sham equations is discussed and shown to be a critical point of basis set approaches to time-dependent density functional theory.
Keywords:FREQUENCY-DEPENDENT POLARIZABILITIES;WAALS DISPERSIONCOEFFICIENTS;CORRECT ASYMPTOTIC-BEHAVIOR;FUNCTIONAL RESPONSETHEORY;DIPOLE POLARIZABILITY;POLYATOMIC-MOLECULES;APPROXIMATION;SYSTEMS;HYPERPOLARIZABILITIES;PHOTOABSORPTION