@article{shrestha_gonzalez-delgado_blew_jakubikova_2014, title={Electronic Structure of Covalently Linked Zinc Bacteriochlorin Molecular Arrays: Insights into Molecular Design for NIR Light Harvesting}, volume={118}, ISSN={["1520-5215"]}, DOI={10.1021/jp507749c}, abstractNote={Pigment-based molecular arrays, especially those based on porphyrins, have been extensively studied as viable components of artificial light harvesting devices. Unlike porphyrins, bacteriochlorins absorb strongly in the NIR, yet little is known of the applicability of covalently linked bacteriochlorin-based arrays in this arena. To lay the foundation for future studies of excited state properties of such arrays, we present a systematic study of the ground state electronic structure of zinc bacteriochlorin (ZnBC) molecular arrays with various linkers and linker attachment sites (meso vs β) employing density functional theory in combination with the energy-based fragmentation (EBF) method, and the EBF with molecular orbitals (EBF-MO) method. We find that the level of steric hindrance between the ZnBC and the linker is directly correlated with the amount of ground sate electronic interactions between the ZnBCs. Low steric hindrance between the ZnBC and the linker found in alkyne-linked arrays results in strongly interacting arrays that are characterized by a decrease in the HOMO-LUMO energy gaps, large orbital energy dispersion in the frontier region, and low ZnBC-linker rotational barriers. In contrast, sterically hindered linkers, such as aryl-based linkers, result in weakly interacting arrays characterized by increased orbital energy degeneracy in the frontier region and high ZnBC-linker rotational barriers. For all linkers studied, the level of steric hindrance decreases when the ZnBCs are linked at the β position. Hence, ZnBC arrays that exhibit strong, weak, or intermediate ground-state electronic interactions can be realized by adjusting the level of steric hindrance with a judicious choice of the linker type and linker attachment site. Such tuning may be essential for design of light harvesting arrays with desired spectral properties.}, number={42}, journal={JOURNAL OF PHYSICAL CHEMISTRY A}, author={Shrestha, Kushal and Gonzalez-Delgado, Jessica M. and Blew, James H. and Jakubikova, Elena}, year={2014}, month={Oct}, pages={9901–9913} }
 @article{bowman_blew_tsuchiya_jakubikova_2013, title={Elucidating Band-Selective Sensitization in Iron(II) Polypyridine-TiO2 Assemblies}, volume={52}, ISSN={["1520-510X"]}, DOI={10.1021/ic4007839}, abstractNote={Iron(II) polypyridines represent a cheaper and nontoxic alternative to analogous Ru(II) polypyridine dyes successfully used as photosensitizers in dye-sensitized solar cells (DSSCs). We employ density functional theory (DFT) and time-dependent DFT (TD-DFT) to study ground and excited state properties of [Fe(bpy)(CN)4](2-), [Fe(bpy-dca)(CN)4](2-), and [Fe(bpy-dca)2(CN)2] complexes, where bpy = 2,2'-bipyridine and dca = 4,4'-dicarboxylic acid. Quantum dynamics simulations are further used to investigate the interfacial electron transfer (IET) between the excited Fe(II) dyes and a TiO2 nanoparticle. All three dyes investigated display two bands in the visible region of the absorption spectrum, with the major transitions corresponding to the metal-to-ligand charge transfer states. The calculated IET rates from the particle states created by the excitation of the lower-energy absorption band are comparable to or slower than the rate of the excited state decay into the nonemissive, metal-centered states of the Fe(II) dyes (∼100 fs), indicating that the IET upon the excitation of this band is unlikely. Several particle states in the higher-energy absorption band display IET rates at or below 100 fs, suggesting the possibility of the IET between the Fe(II)-sensitizer and TiO2 nanoparticle upon excitation with visible light. Our results are consistent with the previous experimental work on Fe(II) sensitizers (Ferrere, S. Chem. Mater. 2000, 12, 1083) and elucidate the band-selective nature of the IET in these compounds.}, number={15}, journal={INORGANIC CHEMISTRY}, author={Bowman, David N. and Blew, James H. and Tsuchiya, Takashi and Jakubikova, Elena}, year={2013}, month={Aug}, pages={8621–8628} }