QM/MM investigation of the degradation mechanism of the electron-transporting layer

The mechanism of charge transfer among tris(8-hydroxyquinolinate)aluminum (Alq₃) molecules in the electron-transporting layer (ETL) under amorphous conditions was theoretically investigated using both quantum mechanical/molecular mechanical (QM/MM) calculations and molecular dynamics (MD) simulations. The rate constant of the electron transfer was estimated for the equilibrated structure taken from the QM/MM MD simulations, based on the hopping model and Marcus theory. It was found that the coordination of a (LiF)₄ cluster in ETL drastically lowers the energy of the lowest unoccupied molecular orbital in the Alq₃ molecule. The small rate constant, namely the slow charge mobility, in ETL is believed to be causally related to the low-lying delocalized unoccupied molecular orbital of Alq₃ coordinated by the (LiF)₄ cluster. The results suggest that their interaction has a considerable influence on efficiency and is attributed in part to ETL degradation in organic light-emitting diodes.     

Role of CH�C�� interaction energy in self-assembled gear-shaped amphiphile molecules: correlated ab initio molecular orbital and density functional theory study

Ab initio molecular orbital and density functional theory calculations with inclusion of dispersion interaction effect are employed to reveal the characteristic features of intermolecular interactions for the molecular capsule (1 ₆) consisting of six gear-shaped amphiphile molecules (1) discovered by Hiraoka et al. (J Am Chem Soc 130:14368?C14369, 2008). The contributions of CH?C?? and ?ШC?? type dispersion energies are found to be indispensable for the formation of hexameric capsule 1 ₆ by the analysis of decomposed interaction energies between fragmented-model species in the 1 molecule. We have also calculated the hexameric capsule (2 ₆) from demethylated 1 molecule (2). Such subtle structural difference induces the different characters of intermolecular interactions, in which the stabilization energy of hexameric 2 ₆ capsule is about 40?kcal/mol smaller than that of the original 1 ₆ capsule, due to the lack of three methyl groups for the CH?C?? interactions in 2 molecules.     

Ab initio electron correlated studies on the intracluster reaction of NO+ (H2O)(n) → H3O+ (H2O)(n-2) (HONO) (n = 4 and 5)

Hydrated nitrosonium ion clusters NO(+)(H(2)O)(n) (n = 4 and 5) were investigated by using MP2/aug-cc-pVTZ level of theory to clarify isomeric reaction pathways for formation of HONO and fully hydrated hydride ions. We found some new isomers and transition state structures in each hydration number, whose lowest activation energies of the intracluster reactions were found to be 4.1 and 3.4 kcal mol(-1) for n = 4 and n = 5, respectively. These thermodynamic properties and full quantum mechanical molecular dynamics simulation suggest that product isomers with HONO and fully hydrated hydride ions can be obtained at n = 4 and n = 5 in terms of excess hydration binding energies which can overcome these activation barriers.     

Polarized SSXANES study of spin ordering in ferromagnetic and paramagnetic phases of La1.2Sr1.65Ca0.15Mn2O7

Spin-selected polarized X-ray absorption near-edge structures (SSXANES) at the Mn K-edge from a bilayer La_1.2Sr_1.65Ca_0.15Mn₂O₇ single crystal have been studied with high resolution, both in the ferromagnetic (15 K) as well as paramagnetic phase (300 K). The orientation-dependent SSXANES spectra show unmistakable temperature dependence as the system makes the ferromagnetic to paramagnetic phase transition. The pre-edge structures are too intense to be ascribed to weak quadrupole transitions and are interpreted in terms of hybridization of Mn 3d orbitals with O2p and Mn 4p orbitals over and above similar onsite hybridization. The results also indicate possible existence of a small local (time-frozen) ferromagnetic ordering in the macroscopically disordered state. Need for further experimental and theoretical work on the SSXANES spectra from the bilayer system is emphasized.     

A metallocene catalyst system for olefin polymerization using a heteropolyacid as the counter-anion

Polymerization of ethylene and propene were conducted with bis(cyclopentadienylzirconium dichloride) (Cp₂ZrCl₂) and ethylenebis(1-indenyl)zirconium dichloride (Et(Ind)₂ZrCl₂) combined with trialkylaluminium compounds using heteropolyacids as the counter-anions, giving linear polyethylene and isotactic polypropene, respectively. No polymer was obtained when using Cp₂Zr(CH₃)₂ instead of Cp₂ZrCl₂. The mechanism of the formation of active species is briefly discussed on the basis of these results.     

Control of photochemistry of stilbazolium ion by adsorption to poly(potassium vinylsulfate) and to hectorite clay

Adsorption or intercalation of trans-1-methyl-4-(2-phenylvinyl)pyridinium ion (stilbazolium ion, SB ( 1 )) to a polyelectrolyte, i. e., poly(potassium vinylsulfate) (PVSK), and to a hectorite clay is studied and its effect on the photochemistry of SB examined. trans-cis Photoisomerization of SB molecularly adsorbed to PVSK proceeds efficiently as with free SB in water, while that of SB molecularly intercalated in the clay is markedly suppressed. Photodimerization proceeds efficiently with SB intercalated in the clay in the aggregated form. Overall photodecoloration, however, proceeds more efficiently with SB adsorbed to PVSK under multiple adsorption conditions apparently due to the higher mobility of PVSK-adsorbed SB compared to that of clay-intercalated SB.     

Recent development in heterogeneous metallocene catalysts

The synthetic methods of heterogeneous metallocene catalysts reported so far in academic journals are summarized together with their catalyst performance. Some of our new results in this field are also described in brief.