Optical Properties of Clusters and Molecules from Real-Time Time-Dependent Density Functional Theory Using a Self-Consistent Field

Abstract

We present a detailed study of optical absorption spectra of finite-size structures, using a method based on time-dependent density-functional theory (TDDFT), which involves a self-consistent field for the propagation of the Kohn–Sham wavefunctions in real-time. Although our approach does not provide a straightforward assignment of absorption features to corresponding transitions between Kohn–Sham orbitals, as is the case in frequency-domain TDDFT methods, it allows the use of larger timesteps while conserving total energy and maintaining stable dipole moment oscillations. These features enable us to study larger systems more efficiently. We demonstrate the efficiency of our method by applying it to a hydrogen-terminated silicon cluster consisting of 364 atoms, with and without P impurities. For cases where direct comparison to experiment can be made, we reproduce the absorption features of fifteen small molecules [(N_2), (O_2), (O_3), (NO_2), (N_2O), (NH_3), (H_2O), (H_2CO), (H_2CO_3), (CO_2), (CH_4), (C_2H_2), (C_2H_4), (C_2H_6), (C_6H_6)] and find generally good agreement with experimental measurements. Our results are useful for the detection and the determination of orientation of these molecules.