Calculating molecular properties in realistic environments
Paper I: Beerepoot, M. T. P., Steindal, A. H., Kongsted, J., Brandsdal, B. O., Frediani, L., Ruud, K., Olsen, J. M. H.: “A polarizable embedding DFT study of one-photon absorption in fluorescent proteins”. Available in Physical Chemistry Chemical Physics 2013, 15:4735–4743. (PDF)
Paper II: Schwabe, T., Beerepoot, M. T. P., Olsen, J. M. H., Kongsted, J.: “Analysis of computational models for an accurate study of electronic excitations in GFP”. Also available in Physical Chemistry Chemical Physics 2015, 17:2582– 2588. (PDF)
Paper III: Beerepoot, M. T. P., Steindal, A. H., Ruud, K., Olsen, J. M. H., Kongsted, J.: “Convergence of environment polarization effects in multiscale modeling of excitation energies.” Also available in Computational and Theoretical Chemistry 2014, 1040: 304–311. (PDF)
Paper IV: Beerepoot, M. T. P., Steindal, A. H., List, N. H., Kongsted, J., Olsen, J. M. H.: “Averaged solvent embedding potential parameters for multiscale modeling of molecular properties.” Also available in Journal of Chemical Theory and Computation 2016, 12(4):1684–1695. (PDF)
Paper V: Beerepoot, M. T. P., Friese, D. H., Ruud, K.: “Intermolecular charge transfer enhances two-photon absorption in yellow fluorescent protein”. Also available in Physical Chemistry Chemical Physics 2014, 16: 5958–5964. (PDF)
Paper VI: Beerepoot, M. T. P., Friese, D. H., List, N. H., Kongsted, J., Ruud, K.: “Benchmarking two-photon absorption cross sections: Performance of CC2 and CAM-B3LYP.” Also available in Physical Chemistry Chemical Physics 2015, 17:19306–19314. (PDF)
Paper VII: List, N. H., Beerepoot, M. T. P., Olsen, J. M. H., Gao, B., Ruud, K., Jensen, H. J. A., Kongsted, J.: “Molecular quantum mechanical gradients within the polarizable embedding approach— Application to the internal vibrational Stark shift of acetophenone.” Also available in Journal of Chemical Physics 2015, 142:034119. (PDF)
ForfatterBeerepoot, Maarten T. P.
This thesis focuses on how absorption properties of molecules are influenced by their environment and how this can be calculated accurately. Calculations have been performed with a polarizable embedding (PE) multiscale model. The environment is described classically by charges and electric multipoles for the permanent electrostatics and polarizabilities for polarization interactions. Density-functional theory (DFT) and approximate singles and doubles coupled-cluster theory (CC2) are used to describe the electronic structure of the molecules. The results indicate that the effects of environmental polarization on electronic and vibrational properties are significant and that the employed PE model is accurate in cases where electrostatic interactions dominate. A large part of the environment needs to be described explicitly for converged molecular properties, especially since polarization interactions range over a long distance. However, accurate embedding parameters for the electrostatic and polarization interactions are important mainly for the closest environment of a chromophore. This enables a reduction of the computational cost of obtaining embedding potentials without sacrificing accuracy. For localized properties, PE is to be preferred over a cluster approach because the latter is severely limited by the possible size of the molecular system. For calculation of two-photon absorption (TPA), DFT and CC2 give qualitatively but not quantitatively similar results. Finally, it is shown that the comparison between calculated TPA cross sections and other experimental or theoretical work is challenging. The presented works contribute to the realistic description of a molecular environment with the accurate prediction of molecular properties in chemical environments as ultimate goal.
ForlagUiT Norges arktiske universitet
UiT The Arctic University of Norway
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