Interpretation of Hund's multiplicity rule for the carbon atom

Hund's multiplicity rule is investigated for the carbon atom using quantum Monte Carlo methods. Our calculations give an accurate account of electronic correlation and obey the virial theorem to high accuracy. This allows us to obtain accurate values for each of the energy terms and therefore to give a convincing explanation of the mechanism by which Hund's rule operates in carbon. We find that the energy gain in the triplet with respect to the singlet state is due to the greater electron-nucleus attraction in the higher spin state, in accordance with Hartree-Fock calculations and studies including correlation. The method used here can easily be extended to heavier atoms.     

Catalytic intermolecular Pauson-Khand-type reaction: strong directing effect of pyridylsilyl and pyrimidylsilyl groups and isolation of Ru complexes relevant to catalytic reaction

Some circumstantial evidence for the directing effect of the 2-pyridylsilyl group in the Ru-catalyzed intermolecular Pauson-Khand-type reaction (PKR) of alkenyl(2-pyridyl)silane, alkyne, and carbon monoxide has been provided. Most importantly, we have succeeded in isolating several monometallic Ru complexes relevant to the catalytic reaction: Ru(vinylsilane)(CO)(3) complexes and ruthenacyclopentene. While the stoichimetric reaction of the Ru(vinylsilane)(CO)(3) complex with an alkyne led to the formation of the corresponding cyclopentenone (PKR product) at 100 degrees C, the ruthenacyclopentene intermediate was quantitatively produced at 50 degrees C. This complex was also converted to a cyclopentenone upon heating at 100 degrees C. Moreover, it was also found that the Ru(vinylsilane)(CO)(3) complex and ruthenacyclopentene serve as catalysts in intermolecular PKR.     

Beam-polarization asymmetries for the p(gamma-->, K+)Lambda and p(gamma-->, K+)Sigma(0) reactions for E(gamma)=1.5-2.4 GeV

Beam polarization asymmetries for the p(gamma-->,K+)Lambda and p(gamma-->,K+)Sigma(0) reactions are measured for the first time for E(gamma)=1.5-2.4 GeV and 0.6相似文献   

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.     

Internal Rotation of the Hydroxyl Group in Isopropanol and the Chirality of the Gauche Form: Fourier Transform Microwave Spectroscopy of (CH(3))(2)CHOD

The rotational spectrum of the deuterated isopropanol (CH(3))(2)CHOD has been observed by Fourier transform microwave spectroscopy and analyzed to yield tunneling splitting of 4431.4613 (17) MHz, between the antisymmetric and the symmetric gauche forms, which is much larger than the 2400 MHz estimated from the internal-rotation potential function reported in the literature. The potential function for the OH internal rotation has been examined in view of the discrepancy between the observed and estimated tunneling splitting, and it was accounted for by taking into account isotope effects on the potential constants. The deuterium quadrupole coupling effect has been included together with the Coriolis terms in the off-diagonal block of the Hamiltonian matrix for the gauche form. The deuterium quadrupole coupling constants obtained for the trans form were employed to calculate the components of the coupling constants as functions of the internal-rotation angle, and the components at around 120 degrees were compared with the values observed for the gauche form, thereby leading to unambiguous determination of the signs of the constants in the off-diagonal block; the signs are not obtainable from an ordinary analysis of the rotational spectra. The chirality of the gauche form was discussed by placing special emphasis on the effect of intermolecular interactions between two chiral molecules. Copyright 2001 Academic Press.     

Effects of Cs treatment on field emission properties of capped carbon nanotubes

Within the methodology [M. Khazaei, A.A. Farajian, Y. Kawazoe, Phys. Rev. Lett. 95 (2005) 177602] based on first-principles electronic structure calculations, the effects of Cs treatment on current emissions and emission patterns of capped carbon nanotubes are considered at low deposition densities when the nanotubes are under an electric field 0.2 V/Å. The results show that the current emission from the cap with one adsorbed Cs is 3.4 times larger than the cap without any Cs. It is 9.6 times larger in the cap with two adsorbed Cs atoms. After Cs deposition the emission patterns become asymmetric (current emission from the carbon atoms located at the topmost pentagon ring close to Cs atoms is larger than the other atomic sites). There are very few localized states on Cs atoms. Hence, although the tunneling probability of electron emission from Cs atoms is significant, there is no current from Cs atoms. In addition, the effect of Cs on work function reduction of nanotubes is explained in terms of Cs deposition densities and the surface dipole moments.     

Optical probe using eccentric optics for optical coherence tomography

We propose and demonstrate an OCT optical probe using eccentric optics. This probe enabled both forward imaging and side imaging by dividing a circular scanning area into two semicircular scanning areas using an external motor to rotate the flexible tube. The outer diameter of the probe was 2.6 mm, and its rigid portion length was 10 mm. The lateral resolution was 23 μm, and the eccentric radius was 1.1 mm. The circumferential length in scanning was 6.9 mm, and the working distance was 5 mm. OCT images of 1.5 mm × 6.9 mm (in tissue, axial × circumference), including forward image and side image, were measured with the axial resolution of 19 μm in air and a frame rate of one frame per second. The epidermis, dermis, and sweat gland of in vivo human ventral finger tips were observed.