Femtosecond intermolecular electron transfer in condensed systems

We have investigated the ultrafast intermolecular electron transfer (ET) from an electron-donating solvent (aniline (AN) or N, N-dimethylaniline (DMA)) to an excited dye molecule (oxazines (Nile blue and oxazine 1) or coumarins). A non-exponential time dependence was observed in AN and can be explained by solvent reorientation and nuclear motion of the reactants. However, in DMA, a single exponential process was observed for Nile blue (160 fs) and oxazine 1 (280 fs), which can be explained by assuming that the rate of ET is limited mainly by ultrafast nuclear motion. A clear substituent effect on intermolecular ET was observed for the 7-aminocoumarins. When the alkyl chain on the 7-amino group is extended and a hexagonal ring with the benzene moiety is formed, the rate of ET is reduced by three orders of magnitude. This effect can be explained by a change in the free energy difference of the reaction and by the vibrational motion of the amino group.     

Codimension Two PL Embeddings of Spheres with Nonstandard Regular Neighborhoods

For a given polyhedron K(?)M,the notation RM(K)denotes a regular neigh- borhood of K in M.The authors study the following problem:find all pairs(m,k) such that if K is a compact k-polyhedron and M a PL m-manifold,then R_M(f(K))≌R_M(g(K))for each two homotopic PL embeddings f,g:K→M.It is proved that R_S~(k 2)(S~k)(?)S~k×D~2 for each k(?)2 and some PL sphere S~k(?)S~(k 2)(even for any PL sphere S~k(?)S~(K 2)having an isolated non-locally flat point with the singularity S~(k-1)(?) S~(k 1)such thatπ_1(S~(k 1)-S~(k-1))(?)Z).     

An Extension of the Conjugate Directions Method With Orthogonalization to Large-Scale Problems With Bound Constraints

In our previous works a new method of conjugate directions for large-scale unconstrained minimization problems has been presented [1, 2]. In the paper this algorithm is extended to minimization problems with bound constraints. Because the linear minimization along the newly found conjugate vector is not needed for constructing the next conjugate vector and one arbitrarily step-size (not necessarily the optimal one) is calculated along this conjugate direction, we are able to incorporate naturally the bound constraints into the algorithm. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Atypical Film-Forming Behavior of Soluble Tetra-3-Nitro-Substituted Copper Phthalocyanine

Thin films of metal phthalocyanines (MPc) are known to exhibit excellent physical properties but poorly controlled morphologies. Therefore, the present work seeks to understand the film growth mechanism of a model compound for potentially usable MPc, specifically, copper tetra(3-nitro-5-tert-butyl)phthalocyanine (CuPc*). The Langmuir-Schaefer (LS) technique was applied to prepare a series of CuPc* films under different processing conditions. The film growth was examined by Brewster angle microscopy (BAM) on the water surface and small-angle X-ray scattering (SAXS) from the solid films. Neutron reflectometry (NR) measurements of the water uptake into the films and computer simulation of hydrated CuPc* were performed to substantiate an idea of colloidal MPc-water aggregates as nanoscale precursors of smooth solid films. This idea appears fruitful in terms of materials chemistry.