title: Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory.
abstract: A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host-guest complex (TTF⊂CBPQT(4+)). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host-guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. However, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.
authors.affiliation: Department of Chemistry, The Pennsylvania State University , 104 Chemistry Building, University Park, Pennsylvania 16802, United States.
authors.forename: Daniel W
authors.initials: DW
authors.lastname: Silverstein
authors.affiliation: William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory , 902 Battelle Boulevard, Richland, Washington 99352, United States.
authors.forename: Niranjan
authors.initials: N
authors.lastname: Govind
authors.affiliation: William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory , 902 Battelle Boulevard, Richland, Washington 99352, United States.
authors.forename: Hubertus J J
authors.initials: HJ
authors.lastname: van Dam
authors.affiliation: Department of Chemistry, The Pennsylvania State University , 104 Chemistry Building, University Park, Pennsylvania 16802, United States.
authors.forename: Lasse
authors.initials: L
authors.lastname: Jensen