caa a22 4500 605513155 CHVBK 20210128100658.0 cr unu---uuuuu 210128e20150501xx s 000 0 eng 10.1007/s00894-015-2676-3 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2676-3 DFT study of zinc, cadmium, mercury, copper, silver, and gold complexes of 21,23-dioxaporphyrin and one-dimensional arrays of those complexes [Elektronische Daten] [Ulises Castillo, Héctor López, Patricia Guadarrama, Serguei Fomine] Complexes of 21,23-dioxaporphyrin with neutral Zn, Cd, Hg, Cu, Ag, and Au atoms as well as some one-dimensional arrays of those complexes containing up to ten repeat units were modeled at the PBE/def2-TZVPP level of theory with D3 empirical dispersion correction. The binding energy between the metal atom and the macrocycle was found to vary from 90kcal/mol for Cu to −14kcal/mol for Hg. Strong charge transfer from the metal to the macrocycle accompanied complex formation. The complexes were able to form dimers and nanoarrays that were held together mostly by dispersion forces. Different types of dimers were studied: face-to-face (F) and two types of parallel-displaced ones. F dimers were calculated to be the lowest-energy structures for Cu and Ag systems. Nanoarray formation was studied for these complexes. The band gaps (E g) of the nanoarrays were found to be smaller than 1 eV, and decreased slightly as the number of repeat units in the nanoaggregates increased. The ionization potentials and electron affinities were greatly affected by the number of repeat units due to the delocalization of polarons over the entire nanoarray. The polaron delocalization and the related reorganization energies depended to a considerable extent on the metal present in the complex. For the studied nanoarrays, the reorganization energies for hole and electron transport decreased linearly with 1/n, where n is the number of repeat units in the nanoaggregate; for an infinitely long chain, the reorganization energy was zero for electron transport and 0.03-0.04eV for hole transport. Springer-Verlag Berlin Heidelberg, 2015 Dioxaporphyrin nationallicence DFT nationallicence Dispersion correction nationallicence Reorganization energy nationallicence Polarons nationallicence Castillo Ulises Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut López Héctor Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut Guadarrama Patricia Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut Fomine Serguei Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-11 1610-2940 21:5<1 2015 21 894 https://doi.org/10.1007/s00894-015-2676-3 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2676-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Castillo Ulises Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut NATIONALLICENCE 700 1- López Héctor Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut NATIONALLICENCE 700 1- Guadarrama Patricia Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut NATIONALLICENCE 700 1- Fomine Serguei Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-11 1610-2940 21:5<1 2015 21 894