An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules

Abstract

Time-dependent density-functional (TDDFT) methods are applied within the adiabatic approximation to a series of molecules including C70. Our implementation provides an efficient approach for treating frequency-dependent response properties and electronic excitation spectra of large molecules. We also present a new algorithm for the diagonalization of large non-Hermitian matrices which is needed for hybrid functionals and is also faster than the widely used Davidson algorithm when employed for the Hermitian case appearing in excited energy calculations. Results for a few selected molecules using local, gradient-corrected, and hybrid functionals are discussed. We find that for molecules with low lying excited states TDDFT constitutes a considerable improvement over Hartree–Fock based methods (like the random phase approximation) which require comparable computational effort.