Ryota Jono

Theoretical Study of the Surface Complex between TiO2 and TCNQ Showing Interfacial Charge-Transfer Transitions

The surface complex of TiO2 nanoparticles and TCNQ was studied using density functional theory (DFT) calculations. The structure of the surface complex was optimized, showing an IR spectrum analogous to the experimental spectrum. From time-dependent DFT calculations based on this optimized structure, we demonstrated that the interfacial charge-transfer transitions from the HOMO of the surface-bound TCNQ molecule to the unoccupied levels of the TiO2 nanocluster occur in the visible to near-IR region.

Remarkable Dependence of the Final Charge Separation Efficiency on the Donor–Acceptor Interaction in Photoinduced Electron Transfer

The unprecedented dependence of final charge separation efficiency as a function of donor-acceptor interaction in covalently-linked molecules with a rectilinear rigid oligo-p-xylene bridge has been observed. Optimization of the donor-acceptor electronic coupling remarkably inhibits the undesirable rapid decay of the singlet charge-separated state to the ground state, yielding the final long-lived, triplet charge-separated state with circa 100% efficiency. This finding is extremely useful for the rational design of artificial photosynthesis and organic photovoltaic cells toward efficient solar energy conversion.

Hysteresis-free perovskite solar cells made of potassium-doped organometal halide perovskite

Potassium-doped organometal halide perovskite solar cells (PSCs) of more than 20% power conversion efficiency (PCE) without I-V hysteresis were constructed. The crystal lattice of the organometal halide perovskite was expanded with increasing of the potassium ratio, where both absorption and photoluminescence spectra shifted to the longer wavelength, suggesting that the optical band gap decreased. In the case of the perovskite with the 5% K+, the conduction band minimum (CBM) became similar to the CBM level of the TiO2-Li. In this situation, the electron transfer barrier at the interface between TiO2-Li and the perovskite was minimised. In fact, the transient current rise at the maximum power voltages of PSCs with 5% K+ was faster than that without K+. It is concluded that stagnation-less carrier transportation could minimise the I-V hysteresis of PSCs.

The origin of the strong interfacial charge-transfer absorption in the surface complex between TiO2 and dicyanomethylene compounds

Interfacial charge transfer transitions between organic and inorganic materials are expected to be a potential photoinduced charge separation mechanism for photoenergy conversions. Recently, we reported that the hybrid material formed from TiO2 nanoparticles and an organic electron acceptor, 7,7,8,8-tetracyanoquinodimethane (TCNQ), shows strong interfacial charge transfer absorption in the visible region. In this work, we have theoretically studied the structure, and electronic and absorption properties in order to clarify the formation mechanism and the origin of the strong interfacial charge transfer absorption. Density functional theory (DFT) calculations employing an anatase Ti14O28H2(OH)2(H2O)2 nano-cluster unraveled that the surface complex is formed by a nucleophilic addition reaction between a surface hydroxyl group of TiO2 and the carbon atom of the methylene moiety in TCNQ with the drastic changes in the structure and electronic properties of TCNQ. In the formation process, owing to the high electron affinity of TCNQ, a negative charge of the surface oxygen atom is transferred to the TCNQ moiety. This leads to a significant electronic hybridization between TiO2 and TCNQ, which is the origin of interfacial charge transfer transitions.

Redox Reaction Mechanisms with Non-triiodide Mediators in Dye-Sensitized Solar Cells by Redox Potential Calculations

We investigate reaction mechanisms of the redox mediators in dye-sensitized solar cells through systematic calculations of redox potentials of possible cobalt complexes and iodides in acetonitrile solution by use of the thermodynamic cycle method with continuum solvent model. The calculated redox potentials were in good agreement with the experimental values, although the experimentalists used different reference electrodes. The maximum open circuit voltage (VOC) of the mediators calculated in this work indicate that the I2(•-)/2I(-) and I2/I2(•-) as well as the net I2/2I(-) redox reactions can dominate at both photoanode and counter-electrode.

Multicanonical ab inito QM/MM molecular dynamics simulation of a peptide in an aqueous environment

We developed a multicanonical ab initio QM/MM molecular dynamics simulation method to enhance conformational sampling of biomolecules in an aqueous environment. We applied this method to an alanine dipeptide immersed in a sphere of explicit water molecules. The peptide and the water molecules were treated by the QM method at the HF/3‐21G level and by the MM method, respectively. The van der Waals interactions between the peptide and the water molecules were calculated at the MM level, while the electrostatic interaction terms between them were incorporated into the QM Hamiltonian to account for the effect of the solvent on the electronic structure of the peptide. The simulation was performed for 1 ns, and a free‐energy map was calculated with respect to the peptide conformation. All the conformations (C5, PII, C7eq, and αR) that have been experimentally suggested to exist in solution formed basins on the free‐energy surface. Analysis of the water distribution revealed that the αR conformation was stabilized by the interaction between the large electric dipole moments of this peptide conformation and the water electric dipole moments, whereas the PII conformation was stabilized by the formation of characteristic hydrogen bonds with the water molecules.

Self‐Organized Superlattice and Phase Coexistence inside Thin Film Organometal Halide Perovskite

Organometal halide perovskites have attracted widespread attention as the most favorable prospective material for photovoltaic technology because of their high photoinduced charge separation and carrier transport performance. However, the microstructural aspects within the organometal halide perovskite are still unknown, even though it belongs to a crystal system. Here direct observation of the microstructure of the thin film organometal halide perovskite using transmission electron microscopy is reported. Unlike previous reports claiming each phase of the organometal halide perovskite solely exists at a given temperature range, it is identified that the tetragonal and cubic phases coexist at room temperature, and it is confirmed that superlattices composed of a mixture of tetragonal and cubic phases are self-organized without a compositional change. The organometal halide perovskite self-adjusts the configuration of phases and automatically organizes a buffer layer at boundaries by introducing a superlattice. This report shows the fundamental crystallographic information for the organometal halide perovskite and demonstrates new possibilities as promising materials for various applications.

Multi-wall effects on the thermal transport properties of nanotube structures

Understanding the role of inter-layer interactions in multi-walled carbon nanotubes is one of the challenges in the design of potential materials because of their large impact on the physical properties of carbon nanotubes. We focused on the thermal properties of double-walled carbon nanotubes (DWCNTs), which are promising materials due to their high durability and thermal efficiency. We investigated the thermal conductance of DWCNTs by using the nonequilibrium Greens function method, and found that the quadratic temperature dependence of the thermal conductance at low temperatures consisted of three regions with different tendencies. Based on analysis of the transmission coefficients and the distribution of the normal modes, the three nonuniform regions were attributed to the energy shifts of the normal modes at the low-energy region. We examined the mechanism of these energy shifts using the coupled vibration model with the parameters from our simulations, and elucidated the multi-wall effects on the thermal transport properties of the nanotube structures. The effects we found demonstrated the significance of tailoring thermal properties to obtain the desired applications.

Electron Transport in a Dioxygenase-Ferredoxin Complex: Long Range Charge Coupling between the Rieske and Non-Heme Iron Center

Dioxygenase (dOx) utilizes stereospecific oxidation on aromatic molecules; consequently, dOx has potential applications in bioremediation and stereospecific oxidation synthesis. The reactive components of dOx comprise a Rieske structure Cys2[2Fe-2S]His2 and a non-heme reactive oxygen center (ROC). Between the Rieske structure and the ROC, a universally conserved Asp residue appears to bridge the two structures forming a Rieske-Asp-ROC triad, where the Asp is known to be essential for electron transfer processes. The Rieske and ROC share hydrogen bonds with Asp through their His ligands; suggesting an ideal network for electron transfer via the carboxyl side chain of Asp. Associated with the dOx is an itinerant charge carrying protein Ferredoxin (Fdx). Depending on the specific cognate, Fdx may also possess either the Rieske structure or a related structure known as 4-Cys-[2Fe-2S] (4-Cys). In this study, we extensively explore, at different levels of theory, the behavior of the individual components (Rieske and ROC) and their interaction together via the Asp using a variety of density function methods, basis sets, and a method known as Generalized Ionic Fragment Approach (GIFA) that permits setting up spin configurations manually. We also report results on the 4-Cys structure for comparison. The individual optimized structures are compared with observed spectroscopic data from the Rieske, 4-Cys and ROC structures (where information is available). The separate pieces are then combined together into a large Rieske-Asp-ROC (donor/bridge/acceptor) complex to estimate the overall coupling between individual components, based on changes to the partial charges. The results suggest that the partial charges are significantly altered when Asp bridges the Rieske and the ROC; hence, long range coupling through hydrogen bonding effects via the intercalated Asp bridge can drastically affect the partial charge distributions compared to the individual isolated structures. The results are consistent with a proton coupled electron transfer mechanism.

Theoretical Verification of Photoelectrochemical Water Oxidation Using Nanocrystalline TiO2 Electrodes

Mesoscopic anatase nanocrystalline TiO2 (nc-TiO2) electrodes play effective and efficient catalytic roles in photoelectrochemical (PEC) H2O oxidation under short circuit energy gap excitation conditions. Interfacial molecular orbital structures of (H2O)3 &OH(TiO2)9H as a stationary model under neutral conditions and the radical-cation model of [(H2O)3&OH(TiO2)9H]+ as a working nc-TiO2 model are simulated employing a cluster model OH(TiO2)9H (Yamashita/Jono’s model) and a H2O cluster model of (H2O)3 to examine excellent H2O oxidation on nc-TiO2 electrodes in PEC cells. The stationary model, (H2O)3&OH(TiO2)9H reveals that the model surface provides catalytic H2O binding sites through hydrogen bonding, van der Waals and Coulombic interactions. The working model, [(H2O)3&OH(TiO2)9H]+ discloses to have a very narrow energy gap (0.3 eV) between HOMO and LUMO potentials, proving that PEC nc-TiO2 electrodes become conductive at photo-irradiated working conditions. DFT-simulation of stepwise oxidation of a hydroxide ion cluster model of OH−(H2O)3, proves that successive two-electron oxidation leads to hydroxyl radical clusters, which should give hydrogen peroxide as a precursor of oxygen molecules. Under working bias conditions of PEC cells, nc-TiO2 electrodes are now verified to become conductive by energy gap photo-excitation and the electrode surface provides powerful oxidizing sites for successive H2O oxidation to oxygen via hydrogen peroxide.