Electronic structures of the highest occupied molecular orbital bands of a pentacene ultrathin film

We report the energy dispersions of the highest occupied molecular orbitals (HOMO)-derived bands of a pentacene (Pn) thin film, whose in-plane structure resembles closely that of the ab plane of a low-density bulk Pn phase. Our present photoemission result indicates that the overlap of the pi-orbitals of adjacent Pn molecules is larger than what was expected from theoretical calculations. Further, of the two HOMO-derived bands, the large dispersion width of the band with higher binding energy suggests that this one mainly contributes to the bandlike charge transport in a Pn crystal.     

Spin distributions in the vibrational excitations of closed-shell nuclei

Self-consistent Hartree-Fock and RPA calculations with the Skyrme-type interaction SGII are used for a systematic investigation of the 1⁺ and the triplet 0^?, 1^?, 2^? states in ⁴⁰Ca and ²⁰⁸Pb. Response functions to spin-dependent multipole operators are calculated and the particle-hole structure of the spin-dependent collective states is studied. Collective spin-dependent 0^? and 1^? states above the giant dipole resonance as well as a collective spin-independent 2^? state (twist mode) are identified. Transition spin and current densities are calculated for the collective excitations and found to be useful for the study of these excitation modes.     

Potential energy curve for ring-opening reactions: comparison between broken-symmetry and multireference coupled cluster methods

The spin-unrestricted Hartree-Fock (UHF)-based coupled cluster singles and doubles (UHF-CCSD) and Mukherjee's state-specific multireference CCSD (MkCCSD) methods are applied to four ring-opening reactions. The spin-restricted Hartree-Fock (RHF)-based CCSD (RHF-CCSD) calculations are also performed for comparison. In the case of the UHF-CCSD method, an approximate spin-projection (AP) method is applied to the broken-symmetry (BS) singlet solution to remove the spin contamination effect. For potential energy curves (PECs) of all reactions presented in this study, the results of RHF-CCSD and UHF-CCSD are substantially different from those of MkCCSD, while the results after the AP method (AP-UCCSD) reproduce the MkCCSD results well. It strongly suggests that the spin contamination effect should be removed by the AP correction even at the UHF-CCSD level to predict reliable energetics of these reactions.     

A free-energy perturbation method based on Monte Carlo simulations using quantum mechanical calculations (QM/MC/FEP method): application to highly solvent-dependent reactions

This study describes the framework of the quantum mechanical (QM)/Monte Carlo (MC)/free‐energy perturbation (FEP) method, a FEP method based on MC simulations using quantum chemical calculations. Because a series of structures generated by interpolating internal coordinates between transition state and reactant did not produce smooth free‐energy profiles, we used structures from the intrinsic reaction coordinate calculations. This method was first applied to the Diels–Alder reaction between methyl vinyl ketone and cyclopentadiene and produced ΔG values of 20.1 and 21.4 kcal mol^?1 in aqueous and methanol solutions, respectively. They are very consistent with the experimentally observed values. The other two applications were the free‐energy surfaces for the Cope elimination of N,N‐dimethyl‐3‐phenylbutan‐2‐amine oxide in aqueous, dimethyl sulfoxide, and tetrahydrofuran solutions, and the Kemp decarboxylation of 6‐hydroxybenzo‐isoxazole‐3‐carboxylic acid in aqueous, dimethyl sulfoxide, and CH₃CN solutions. The calculated activation free energies differed by less than 1.8 kcal mol^?1 from the experimental values for these reactions. Although we used droplet models for the QM/MC/FEP simulations, the calculated results for three reactions are very close to the experimental data. It was confirmed that most of the interactions between the solute and solvents can be described using small numbers of solvent molecules. This is because a few solvent molecules can produce large portions of the solute–solvent interaction energies at the reaction centers. When we confirmed the dependency on the droplet sizes of solvents, the QM/MC/FEP for a large droplet with 106 water molecules produced a ΔG value similar to the experimental values, as well as that for a small droplet with 34 molecules. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Enhancement in the rate of conversion of peptide Cys-Pro esters to peptide thioesters by structural modification

We previously reported that the peptide containing a Cys-Pro ester (CPE) moiety is spontaneously transformed into a peptide thioester via an N to S acyl shift followed by diketopiperazine formation. In an attempt to identify more reactive structures for the formation of a peptide thioester, we modified the CPE structure, in which the Pro residue in the CPE moiety was replaced with N-substituted glycine derivatives. These peptides were transformed into a peptide thioester more rapidly. Alternatively, the addition of an amino acid residue at the C-terminus of the CPE moiety also accelerated thioester formation.     

Dendritic folate rosettes as ion channels in lipid bilayers

The self-assembly of folate dendrimers into pi-stacked supramolecular rosettes is shown to produce ion channels in planar and spherical lipid bilayer membranes. The found ion channels are small, quite homogeneous, long-lived, ohmic, cation selective (Eisenman I), and blockable by the permeant cation.     

A numerical study of 3D natural convection in a cube: effects of the horizontal thermal boundary conditions

A high-resolution, three-dimensional finite-difference numerical study of natural convection flows of a viscous fluid in a differentially heated cubical box is reported. The vertical sidewalls of the enclosure are maintained at constant temperatures of different values. The other vertical walls (the end walls) are thermally insulated. For the horizontal walls, two kinds of thermal boundary conditions are specified: adiabatic and perfectly conducting. Computations have been performed for an air-filled cavity for Rayleigh numbers of 10⁵ and 10⁶. The specific effects of the horizontal thermal boundary conditions on the flow structure are examined in detail. In the case of conducting walls, heat transfer through the horizontal walls enhances the convective flow activities. The numerically predicted velocity and temperature profiles in the symmetry planes are consistent with previous experimental measurements and computations.     

A study on the effect of filling factor for laser action in dielectric random media

In a random system composed of dielectric materials, laser action is expected to occur from the light localization caused by multiple scattering and interference effect. The wavelengths at which the laser oscillation occurs in random media depend on the mean free path of continuous scattering. Since the mean free path of continuous scattering is dependent on the filling factor, it is important to investigate systematically the effect of the filling factor for the laser action. In the present study, we calculate the Poynting vectors of the light emitted from two-dimensional random media consisting of dielectric rods with population inversion modeled by the negative imaginary part of relative permittivity. The spectra of the radiated Poynting vectors from the two-dimensional random media are shown for several different filling factors and for various values of population inversion. We try to find laser generation which occurs at low population inversion and discuss about the threshold of laser action occurring in dielectric structures with different filling factors. We also study the spacial distribution of the electric field amplitude in several frequency regions where light strongly amplifies.     

Magnetic structures of exchange bias Ni/FeF2(1 1 0) interface

Electronic and magnetic structures of ferromagnetic (FM)/antiferromagnetic (AFM), Ni/FeF₂(1 1 0), with a compensated AFM interface are investigated by using the full-potential linearized augmented plane-wave method. We find that magnetic structures at the AFM interface are perturbed by a contact with the FM material, where the superexchange interaction through the interface F excites and induces a small net moment at the AFM interface. These results predicted may play an important role for explaining the exchange bias in this system, and rule out the exchange bias mechanisms with the spin-flop coupling and the magnetic moment reorientation.