@misc{MegowRoehrSchmidtamBuschetal.2015, author = {Megow, J{\"o}rg and R{\"o}hr, Merle I. S. and Schmidt am Busch, Marcel and Renger, Thomas and Mitrić, Roland and Kirstein, Stefan and Rabe, J{\"u}rgen P. and May, Volkhard}, title = {Site-dependence of van der Waals interaction explains exciton spectra of double-walled tubular J-aggregates}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-79978}, pages = {6741 -- 6747}, year = {2015}, abstract = {The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.}, language = {en} } @article{MegowRoehrSchmidtamBuschetal.2015, author = {Megow, J{\"o}rg and R{\"o}hr, Merle I. S. and Schmidt am Busch, Marcel and Renger, Thomas and Mitrić, Roland and Kirstein, Stefan and Rabe, J{\"u}rgen P. and May, Volkhard}, title = {Site-dependence of van der Waals interaction explains exciton spectra of double-walled tubular J-aggregates}, series = {Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies}, volume = {17}, journal = {Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies}, number = {10}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9084}, doi = {10.1039/c4cp05945j}, pages = {6741 -- 6747}, year = {2015}, abstract = {The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.}, language = {en} } @article{MegowRoehrBuschetal.2015, author = {Megow, J{\"o}rg and R{\"o}hr, Merle I. S. and Busch, Marcel and Renger, Thomas and Mitric, Roland and Kirstein, Stefan and Rabe, J{\"u}rgen P. and May, Volkhard}, title = {Site-dependence of van der Waals interaction explains exciton spectra of double-walled tubular J-aggregates}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {17}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {10}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c4cp05945j}, pages = {6741 -- 6747}, year = {2015}, abstract = {The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.}, language = {en} } @unpublished{MegowKoerzdoerferRengeretal.2015, author = {Megow, J{\"o}rg and K{\"o}rzd{\"o}rfer, Thomas and Renger, Thomas and Sparenberg, Mino and Blumstengel, Sylke and May, Volkhard}, title = {Reply to "Comment on 'Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction"}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {32}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b05536}, pages = {18818 -- 18820}, year = {2015}, language = {en} } @article{MegowKoerzdoerferRengeretal.2015, author = {Megow, J{\"o}rg and K{\"o}rzd{\"o}rfer, Thomas and Renger, Thomas and Sparenberg, Mino and Blumstengel, Sylke and Henneberger, Fritz and May, Volkhard}, title = {Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {10}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b01587}, pages = {5747 -- 5751}, year = {2015}, abstract = {We propose a new approach for calculating the change of the absorption spectrum of a molecule when moved from the gas phase to a crystalline morphology. The so-called gas-to-crystal shift Delta epsilon(m) is mainly caused by dispersion effects and depends sensitively on the molecules specific position in the nanoscopic setting. Using an extended dipole approximation, we are able to divide Delta epsilon(m)= -QW(m) in two factors, where Q depends only on the molecular species and accounts for all nonresonant electronic transitions contributing to the dispersion while W-m is a geometry factor expressing the site dependence of the shift in a given molecular structure. The ability of our approach to predict absorption spectra is demonstrated using the example of polycrystalline films of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI).}, language = {en} } @article{FriedlRengerBerlepschetal.2016, author = {Friedl, Christian and Renger, Thomas and Berlepsch, Hans V. and Ludwig, Kai and Schmidt am Busch, Marcel and Megow, J{\"o}rg}, title = {Structure Prediction of Self-Assembled Dye Aggregates from Cryogenic Transmission Electron Microscopy, Molecular Mechanics, and Theory of Optical Spectra}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {120}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.6b05856}, pages = {19416 -- 19433}, year = {2016}, abstract = {Cryogenic transmission electron microscopy (cryo-TEM) studies suggest that TTBC molecules self-assemble in aqueous solution to form single-walled tubes with a diameter of about 35 A. In order to reveal the arrangement and mutual orientations of the individual molecules in the tube, we combine information from crystal structure data of this dye with a calculation of linear absorbance and linear dichroism spectra and molecular dynamics simulations. We start with wrapping crystal planes in different directions to obtain tubes of suitable diameter. This set of tube models is evaluated by comparing the resulting optical spectra with experimental data. The tubes that can explain the spectra are investigated further by molecular dynamics simulations, including explicit solvent molecules. From the trajectories of the most stable tube models, the short-range ordering of the dye molecules is extracted and the optimization of the structure is iteratively completed. The final structural model is a tube of rings with 6-fold rotational symmetry, where neighboring rings are rotated by 30 and the-transition dipole moments of the chromophores form an angle of 74 with respect to the symmetry axis of the tube. This model is in agreement with cryo-TEM images and can explain the optical spectra, consisting of a sharp red-shifted J-band that is polarized parallel to to the symmetry axis of the tube and a broad blue-shifted H-band polarized perpendicular to this axis. The general structure of the homogeneous spectrum of this hybrid HJ-aggregate is described by an analytical model that explains the difference in redistribution of oscillator strength inside the vibrational manifolds of the J- and H-bands and the relative intensities and excitation energies of those bands. In addition to the-particular system investigated here, the present methodology can be expected to aid the structure prediction for a wide range of self-assembled dye aggregates.}, language = {en} }