Density Functional Theory-Based Molecular Modeling: Verification of Decisive Roles of Van der Waals Aggregation of Triiodide Ions for Effective Electron Transfer in Wet-Type N3-Dye-Sensitized Solar Cells

Abstract

Density functional theory-based molecular modeling (DFT/MM) validates that KI and I2 undergo exothermic van der Waals (vdW) aggregation in acetonitrile (AN) or in the presence of 4-tert-butylpyridine (TBP), forming potassium triiodide (KI3) and, further mutual vdW aggregation leads to the formation of (KI3)2 and AN, (KI3)2 and (AN)2 and (KI3)2 and TBP in the AN-based Dye sensitized solar cells (DSSC) electrolytes. All KI3 aggregates have a very low energy gap, 0.17 eV, 0.14 eV and 0.05 eV of lowest unoccupied molecular orbital (LUMO) + 1 and LUMO, respectively, verifying efficient electron diffusion in μm-thick DSSC electrolytes. Hydrogen-bonding aggregation of anatase TiO2 model, Ti9O18H and OH, with N3 (proton) dye is also validated by DFT/MM, and the energy structure verifies unidirectional electron flow from highest occupied molecular orbital (HOMO) on thiocyanide (SCN) groups of N3 dye to LUMO on the TiO2 model at the aggregates. Further, DFT/MM for the aggregation of K+I3− with N3 verifies the most exothermic formation of the aggregate of N3 (proton) and K+I3−. The UV-Vis spectra of N3 (proton) and K+I3− is consistent with reported incident photocurrent efficiency (IPCE) action spectra (λ = 450–800 nm) of N3-sensitized DSSC, verifying that the N3 dye of N3 (proton) and K+I3− becomes an effective sensitizer in the anode / TiO2 / N3 (proton) / KI/I2 / acetonitrile (AN) / cathode structured DSSC. The energy structure of LUMO and LUMO + 1 of the aggregates, Ti9O18H and OH and N3 (proton), N3 and K+I3−, (KI3)2 and AN and (KI3)2 and TBP verifies high IPCE photocurrent and effective electron diffusion via KI3-aggregates in the DSSC of Ti9O18H and OH and N3 (proton) and K+I3−.

Review on the Revolution of Polymer Electrolytes for Dye-Sensitized Solar Cells

“…Besides the size of cation/anion and their lattice energy, we can also investigate electrolyte’s properties using computational and modeling methods to understand its fundamentals. For example, density functional theory (DFT) was reported by Yanagisawa and Yanagida as a useful characterization for verifying the electrical conductivity properties of the salt . This DFT characteristic is based on molecular orbital (MO) modeling of the electron-carrying state radical anions of the salt packing unit.…”

“…For example, density functional theory (DFT) was reported by Yanagisawa and Yanagida as a useful characterization for verifying the electrical conductivity properties of the salt. 163 This DFT characteristic is based on molecular orbital (MO) modeling of the electron-carrying state radical anions of the salt packing unit. It has also been described that DFT and MM apply to molecular aggregates, which are induced by van der Waals (vdW) force (including hydrogen bonding and Coulomb interactions).…”

Improved Recovery and Selectivity of Lanthanide-Ion-Binding Cyclic Peptide Hosts by Changing the Position of Acidic Amino Acids

“…Our cyclic peptides contain 11 amino acids, except for 2-cysteine, which means that 11 11 sequence patterns exist, so the application of such a high-cost MD simulation method for sequence screening/performance prediction is difficult. However, since a DFT calculation analyzing parameters such as molecular structure, bonding, electron negativity, dipole moment (DM), and HOMO (Highest Occupied Molecular Orbital) /LUMO (Lowest Unoccupied Molecular Orbital) can be carried out quickly using personal computers [37], the utilization of such parameters is expected as the candidates of the present screening method.…”