On Koopmans' theorem in density functional theory

This paper clarifies why long-range corrected (LC) density functional theory gives orbital energies quantitatively. First, the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies of typical molecules are compared with the minus vertical ionization potentials (IPs) and electron affinities (EAs), respectively. Consequently, only LC exchange functionals are found to give the orbital energies close to the minus IPs and EAs, while other functionals considerably underestimate them. The reproducibility of orbital energies is hardly affected by the difference in the short-range part of LC functionals. Fractional occupation calculations are then carried out to clarify the reason for the accurate orbital energies of LC functionals. As a result, only LC functionals are found to keep the orbital energies almost constant for fractional occupied orbitals. The direct orbital energy dependence on the fractional occupation is expressed by the exchange self-interaction (SI) energy through the potential derivative of the exchange functional plus the Coulomb SI energy. On the basis of this, the exchange SI energies through the potential derivatives are compared with the minus Coulomb SI energy. Consequently, these are revealed to be cancelled out only by LC functionals except for H, He, and Ne atoms.     

Structure-driven nonlinear instability as the origin of the explosive reconnection dynamics in resistive double tearing modes

The onset of abrupt magnetic reconnection events, observed in the nonlinear evolution of double tearing modes (DTM), is investigated via reduced resistive magnetohydrodynamic simulations. We have identified the critical threshold for the parameters characterizing the linear DTM stability leading to the bifurcation to the explosive dynamics. A new type of secondary instability is discovered that is excited once the magnetic islands on each rational surface reach a critical structure characterized here by the width and the angle rating their triangularization. This new instability is an island structure-driven nonlinear instability, identified as the trigger of the subsequent nonlinear dynamics which couples flow and flux perturbations. This instability only weakly depends on resistivity.     

High pressure studies of viscosity effects on isomerization

Abstract

The viscosity dependence of the isomerization process with comparatively low potential barrier was studied as a model of one-dimensional barrier crossing.

We found that the ground-state isomerization of DODCI fails to fit the Kramers equation. We analyzed this non-Kramers behavior by means of an approach of frequency dependent friction.     

Commutativity in special unitary groups at odd primes

It is a classical result by Bott that SU(s) and SU(t) homotopy commute in SU(n) if and only if s+t?n. We consider the p-localization analog of this problem and give an answer at odd primes.     

In-flight (K~-,N) Reactions for Study of Kaon-nucleus Interaction

We would like to emphasize that the in-flight (K~-,N) reactions are particularly useful for the study of the K-nucleus interaction.Since the reaction mechanism is well known,there is little ambiguity to derive the K-nucleus interaction from the measured missing mass spectra.Here we discuss the missing mass spectra of the (K~-,N) reactions on the ~(12)C and ~(16)O targets.The spectra show an appreciable amount of strength below the K-nucleus threshold which indicates that the K-nuclear potential is strongly attractive.Comparison of the missing mass spectra with theoretical calculations leads to a potential depth of around-190 MeV for the ~(12)C(K~-,n) reaction.A less deep potential of around-160 MeV reproduces well that of the ~(12)C(K~-,p) reaction.The difference can be due to isospin dependence of the interaction.Our data show that the K-nucleus potential is very deep to realize kaon condensation in the core of neutron stars.     

Preparation of highly dispersible and tumor-accumulative, iron oxide nanoparticles Multi-point anchoring of PEG-b-poly(4-vinylbenzylphosphonate) improves performance significantly

This paper describes the preparation of iron oxide nanoparticles, surface of which was coated with extremely high immobilization stability and relatively higher density of poly(ethylene glycol) (PEG), which are referred to as PEG protected iron oxide nanoparticles (PEG-PIONs). The PEG-PIONs were obtained through alkali coprecipitation of iron salts in the presence of the PEG-poly(4-vinylbenzylphosphonate) block copolymer (PEG-b-PVBP). In this system, PEG-b-PVBP served as a surface coating that was bound to the iron oxide surface via multipoint anchoring of the phosphonate groups in the PVBP segment of PEG-b-PVBP. The binding of PEG-b-PVBP onto the iron oxide nanoparticle surface and the subsequent formation of a PEG brush layer were proved by FT-IR, zeta potential, and thermogravimetric measurements. The surface PEG-chain density of the PEG-PIONs varied depending on the [PEG-b-PVBP]/[iron salts] feed-weight ratio in the coprecipitation reaction. PEG-PIONs prepared at an optimal feed-weight ratio in this study showed a high surface PEG-chain surface density (≈0.8 chainsnm(-2)) and small hydrodynamic diameter (<50 nm). Furthermore, these PEG-PIONs could be dispersed in phosphate-buffered saline (PBS) that contains 10% serum without any change in their hydrodynamic diameters over a period of one week, indicating that PEG-PIONs would provide high dispersion stability under in vivo physiological conditions as well as excellent anti-biofouling properties. In fact we have confirmed the prolong blood circulation time and facilitate tumor accumulation (more than 15% IDg(-1) tumor) of PEG-PIONs without the aid of any target ligand in mouse tumor models. The majority of the PEG-PIONs accumulated in the tumor by 96 h after administration, whereas those in normal tissues were smoothly eliminated by 96 h, proving the enhancement of tumor selectivity in the PEG-PION localization. The results obtained here strongly suggest that originally synthesized PEG-b-PVBP, having multipoint anchoring character by the phosphonate groups, is rational design for improvement in nanoparticle as in vivo application. Two major points, viz., extremely stable anchoring character and dense PEG chains tethered on the nanoparticle surface, worked simultaneously to become PEG-PIONs as an ideal biomedical devices intact for prolonged periods in harsh biological environments.     

Communication: a new hybrid exchange correlation functional for band-gap calculations using a short-range Gaussian attenuation (Gaussian-Perdue-Burke-Ernzerhof)

We have developed a new hybrid functional [Gaussian-Perdue-Burke-Ernzerhof (Gau-PBE)] that is suitable for the calculation of solid state bandgaps using a periodic boundary condition. The characteristic of this functional is the use of a Gaussian attenuation scheme (Gau) to include a short-range Hartree-Fock (HF) exchange. This new functional can perform barrier height calculations with an accuracy comparable to the middle-range hybrid functional and bandgap calculations with an accuracy comparable to the Heyd-Scuseria-Ernzerhof (HSE) functional. However, the point is that the performance can be achieved using a Gaussian HF exchange, while the HISS functional calculates twice HF-exchange integrations using an error function to obtain both performances. In addition, Gau-PBE functional can decrease the time cost of bandgap calculations by an average of 40% compared to the HSE functional.     

An examination of density functionals on aldol, Mannich and ��-aminoxylation reaction enthalpy calculations

The reaction enthalpies of aldol, Mannich and ??-aminoxylation reactions were calculated by density functional theory (DFT) using long-range-corrected (LC), hybrid B3LYP and other up-to-date functionals to show why conventional DFT including B3LYP has given poor enthalpies for these reactions. As a result, we found that long-range exchange interactions significantly affect the reaction enthalpies. We therefore proposed that the poor enthalpies of B3LYP are due to its insufficient long-range exchange effect. On the other hand, LC functionals accurately reproduce reaction enthalpies for these reactions. However, we noticed that even LC functionals present poor reaction enthalpies for specific reactions, in which many branches are produced or very small molecules such as methane molecule participate.