title: Comparison of Real-Time and Linear-Response Time-Dependent Density Functional Theories for Molecular Chromophores Ranging from Sparse to High Densities of States.
abstract: We assess the performance of real-time time-dependent density functional theory (RT-TDDFT) for the calculation of absorption spectra of 12 organic dye molecules relevant to photovoltaics and dye-sensitized solar cells with 8 exchange-correlation functionals (3 traditional, 3 global hybrids, and 2 range-separated hybrids). We compare the calculations with traditional linear-response (LR) TDDFT and experimental spectra. In addition, we demonstrate the efficacy of the RT-TDDFT approach to calculate wide absorption spectra of two large chromophores relevant to photovoltaics and molecular switches. RT-TDDFT generally requires longer simulation times, compared to LR-TDDFT, for absorption spectra of small systems. However, it becomes more effective for the calculation of wide absorption spectra of large molecular complexes and systems with very high densities of states.
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Samat
authors.initials: S
authors.lastname: Tussupbayev
authors.affiliation: Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory , Richland, Washington 99338, United States.
authors.forename: Niranjan
authors.initials: N
authors.lastname: Govind
authors.affiliation: Department of Chemistry and Center for Computation & Technology, Louisiana State University , Baton Rouge, Louisiana 70803, United States.
authors.forename: Kenneth
authors.initials: K
authors.lastname: Lopata
authors.affiliation: Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer