Hh. Heinze et al., An efficient method for calculating molecular excitation energies by time-dependent density-functional theory, J CHEM PHYS, 113(6), 2000, pp. 2088-2099
We present a new efficient method for determining excitation energies and o
scillator strengths of molecules which is based on time-dependent density f
unctional theory (TDDFT). It yields the valence excitation spectrum of a mo
lecule at a fraction of the computational effort necessary for the correspo
nding ground state calculation. The efficiency of the method originates in
the extensive use of auxiliary basis sets. Nevertheless this approach does
not lead to significant inaccuracies. The method is applied to benzene, nap
htalene, and the higher linearly annelated polycyclic aromatic hydrocarbons
anthracene to heptacene. Features and trends in the excitation spectra of
these aromatic hydrocarbons are well described by the new TDDFT method. The
standard basis sets commonly used in TDDFT based procedures are found to b
e inadequate for an accurate treatment of excitations into Rydberg-type sta
tes. (C) 2000 American Institute of Physics. [S0021- 9606(00)30530-X].