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Calculations of nonlinear response properties using the intermediate state representation and the algebraic-diagrammatic construction polarization propagator approach: Two-photon absorption spectra

2012; American Institute of Physics; Volume: 136; Issue: 6 Linguagem: Inglês

10.1063/1.3682324

1520-9032

Stefan Knippenberg, Dirk R. Rehn, Michael Wormit, Jan Hendrik Starcke, Irina L. Rusakova, А. Б. Трофимов, Andreas Dreuw,

Advanced Chemical Physics Studies

An earlier proposed approach to molecular response functions based on the intermediate state representation (ISR) of polarization propagator and algebraic-diagrammatic construction (ADC) approximations is for the first time employed for calculations of nonlinear response properties. The two-photon absorption (TPA) spectra are considered. The hierarchy of the first- and second-order ADC/ISR computational schemes, ADC(1), ADC(2), ADC(2)-x, and ADC(3/2), is tested in applications to H2O, HF, and C2H4 (ethylene). The calculated TPA spectra are compared with the results of coupled cluster (CC) models and time-dependent density-functional theory (TDDFT) calculations, using the results of the CC3 model as benchmarks. As a more realistic example, the TPA spectrum of C8H10 (octatetraene) is calculated using the ADC(2)-x and ADC(2) methods. The results are compared with the results of TDDFT method and earlier calculations, as well as to the available experimental data. A prominent feature of octatetraene and other polyene molecules is the existence of low-lying excited states with increased double excitation character. We demonstrate that the two-photon absorption involving such states can be adequately studied using the ADC(2)-x scheme, explicitly accounting for interaction of doubly excited configurations. Observed peaks in the experimental TPA spectrum of octatetraene are assigned based on our calculations.