Transport of excitation energy in a doped molecular aggregate. III. numerical investigation of exciton hopping with various exciton-depleting processes

A brute-force numerical investigation has been carried out on the hopping of excitons in a three-dimensional molecular aggregate. Possibilities of vibronic decay, rapid chemical reactions of saturated species, radiative decay of overpopulated molecules, and cooperative chemical reactions involving saturated exciton populations on traps of two different types have been considered. Investigation have been performed with two types of initial distribution of excitons—facial and random—and for 10,000 or, sometimes, for 20,000 time steps each of duration 1ps. Several interesting observations have been made from this computer experiment: (1) The total number of occurrences of fast reactions depends upon the initial distribution of excitons. (2) It decreases if other exciton depleting processes are at work. (3) It also depends on the pattern of placement of traps. (4) The location of impurities also affects the rate of occurrence of these reactions. Thus, more reactions occur when the excitons are initially concentrated on one face and traps are suitably located on the path of flow of these excitons. A random initial distribution tends to equilibrate the excitons quickly over all the lattice points, thus giving rise to fewer reactions. (5) The number of reactions need not necessarily increase with the number of reaction centers; in fact, it decreases as more centers are added when the supply of excitons is severely limited. (6) A Complicated dynamics results when different types of additional processes, viz., enhanced fluorescence, radiative emissions, and cooperative chemical reactions are simultaneously allowed. The cooperative process has been clearly found to dominate. A first-order rate constant of about 10⁸ s-¹ has been calculated for the occurrence of the cooperative process. This rate is affected when other nonconserving processes are switched on. Observations (1), (4), and (5) are the most important conclusions of our work. They lie outside the scope of traditional models such as the random walk model, the diffusion model, and the lattice model for the migration of excitons in a molecular aggregate. © 1993 John Wiley & Sons, Inc.     

Transformed Dirac equation for the hydrogen atom,comparison with previous approaches in momentum space,and the anomalous Zeeman effect in momentum representation

The solution of a unitarily transformed Dirac equation for the hydrogenic electron in zero magnetic field is investigated here. The momentum‐space representation is adopted as a natural recourse. The spinor part of the transformed wavefunction in momentum space can be easily prescribed for a central potential. Hence, for the Coulomb potential, a pair of equations is obtained for the radial components in momentum space. It is shown that starting from these radial equations, one can recover the equations previously derived by Rubinowicz, Lévy, and Lombardi for the problem of the Dirac hydrogen atom in momentum space. This establishes equivalence among different approaches based on the momentum representation, including the current treatment. The recovery of the equations due to Rubinowicz permits the exact eigenvalues to be written down and exact expressions to be derived for the radial components of the transformed wavefunction in momentum space. A new approach is adopted to carry out a reduction to the nonrelativistic regime and the nonrelativistic limit. At first the transformed momentum‐space equation for the hydrogen atom is rewritten in terms of the hyperspherical coordinates. The zeroth‐order solutions of the new equation are recovered in the limit c → ∞ where c is the speed of light. These are manifestly separable into positive‐ and negative‐energy forms. For positive energy, these solutions have nonvanishing upper components that are two‐component spinors. The latter exactly correspond to the single‐component, nonrelativistic, momentum‐space solutions derived by Fock. It is shown that when the upper component is corrected through first order in v²/c² but the separability is still maintained for the transformed wavefunction, one retrieves the Pauli equation in momentum space. It is also shown that for a hydrogen atom placed in a uniform magnetic field, the nonvanishing momentum‐space matrix elements representing the anomalous Zeeman effect have a simple form, namely, the product of a radial integral and an angular integral. These integrals are equal to the well‐known radial and angular integrals in coordinate representation. The matrix elements can be easily evaluated. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Synthesis of the southern furan segment of furanocembranoids

Abstract

A convergent synthesis of the southern furan segment of novel furanocembranoids from Croton oblongifolius has been accomplished involving silver-catalyzed cyclization of alkynyl diol as the key step towards 2, 5-disubstituted furan ring formation.     

Studies on metal — protein interactions: Inter-comparison among various approaches

Binding ability of mercury, thallium, lead and bismuth with Erythrina variegata seed protein have been investigated using tracer packet technique. Due to the lack of standard methods, inter-comparisons have been made among three different approaches, like trichloroacetic acid (TCA) precipitation, isoelectric precipitation and dialysis of protein after incubation with the metals. Good agreement was observed for all the cases except that of lead.     

Group 6 tetracarbonyl complexes of N-[(2-pyridyl)methyliden]-α (or β)-aminonaphthalene: Spectral characterization,electrochemistry, solvatochromism and photophysical studies

A new series of group 6 carbonyl complexes of N-[(2-pyridyl)methyliden]-α (or β)-aminonaphthalene (α/β-NaiPy) are described in this work. The complexes are formulated as cis-[M(CO)₄(α/β-NaiPy)] by elemental, mass and other spectroscopic data. The complexes show emission spectra at room temperature and their quantum yield lies between 0.4 and 0.5. All the complexes exhibit negative solvatochromism. Cyclic voltammetry shows metal centred oxidation and ligand reductions.     

Bond dissociation energies and bond orders for diatomic alkali halides

The bond dissociation energies for Alkali halides have been estimated based on the derived relations: $$\begin{gathered} D_{AB} = \bar D_{AB} + 31.973{\text{ e}}^{0.363\Delta x} {\text{ and}} \hfill \\ D_{AB} = \bar D_{AB} (1 - 0.2075\Delta xr_e ) + 52.29\Delta x, \hfill \\ \end{gathered} $$ where \(\bar D_{AB} = (D_{AA} \cdot D_{BB} )^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} \) , Δx represents Pauling electronegativity differences x(_A ?x_B) and r _e is the internuclear distance. A simplified formula relating bond orders, q, to spectroscopic constants is suggested. The formula has the form q = 1.5783 × 10^?3 (ω _e ² r_e/ B_e)^1/2. The ambiguity arising from the Parr and Borkman relation is discussed. The present study supports the view of Politzer that q/(0.5r _e)² is the correct definition of bond order. The estimated bond energies and bond orders are in reasonably good agreement with the literature values. The bond energies estimated with the relations we suggested, for alkali halides give an error of 4.5% and 5.3%, respectively. The corresponding error associated with Pauling's equation is 40.2%.     

Designer ribozymes: programming the tRNA specificity into flexizyme

Fx3 is an artificial ribozyme with the ability to aminoacylate various tRNAs with phenylalanine and its nonnatural derivatives. Herein we report a simple strategy to build tRNA specificity into the generic Fx3, by appending to its 3'-end a tRNA-specific sequence (TSS), which is complementary to the acceptor stem of the cognate tRNA. This new designer ribozyme, referred to as Fx10, is able to recognize its cognate tRNA via a 10-base-pair interaction that is formed after the invasion of the tRNA acceptor stem by the TSS. We have demonstrated that Fx10 can aminoacylate its cognate tRNA with a high degree of specificity and also discriminate against the noncognate tRNAs. Because the tRNA specificity can be easily programmed into Fx10, it is a custom-made catalyst to generate nonnatural aminoacyl-tRNAs.     

Investigation of the reactions of fluorinated isatins and N-acetylisatins with thiocarbohydrazide: Synthesis of a novel spiro system: 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione

A novel system 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione has been synthesized by the treatment of fluorinated isatins with thiocarbohydrazide in aqueous ethanolic medium. Under exactly similar conditions, N-acetylisatin gave exclusively thiocarbohydrazone. The spiro product, on treatment with acetic acid, gave fluorinated isoindigo. Characterization of these products have been done by elemental analyses, ir, pmr and mass spectral studies.     

Near-Dirac–Hartree–Fock results for first-row atoms calculated with GTO basis sets

Relativistic basis sets for first-row atoms have been constructed by using the near-Hartree–Fock (nonrelativistic) eigenvectors calculated by Partridge. These bases generate results of near-Dirac–Hartree–Fock quality. Relativistic total and orbital energies, relativistic corrections to the total energy, and magnetic interaction energies for the first-row atoms have been presented. The smallest Gaussian expansions (13s8 p expansions) yield Dirac–Hartree–Fock total energies accurate through six significant digits, while the largest expansions (18s13p expansions) give these energies accurate through seven significant digits. These results are more accurate than some of the results reported earlier, particularly for the open-shell atoms, indicating that the basis employed is reasonably economical for relativistic calculations. © 1995 John Wiley & Sons, Inc.     

A study of 1O2 production by immobilized sensitizer outside the solution. Measurement of 1O2 generation

Abstract— Recently, a new technique of ¹O₂ generation has been described by Midden and Wang. The sensitizer is immobilized on silica gel particles which are attached on one surface of a glass plate which is placed, sensitizer-side down, above a solution leaving a small air space between the sensitizer and the solution. Applying the principle of the technique, i.e. generation of ¹O₂ in the gas phase above the solution, we first improved the long-term stability of the dye (rose bengal) by using double stock transparent tape instead of rubber cement. Under these conditions, although the initial rate of production was higher in rubber cement, the rate of production reached a plateau after 30 min, whereas with double stick transparent tape, the rate of generation was linear up to 100 min. This result was explained by the fact that silica glass beads are embedded in the cement which could lead to the bleaching reaction of the dye. Different reactions have been investigated, the bleaching of N,N-dimethyl-4-nitrosoaniline (RNO) in the presence of imidazole, destruction of anthracenedipropionic acid, formation of a stable nitroxide from a sterically hindered secondary amine and the influence of pH on the nitroxide yield. The yield was measured to be 5 × 10¹² molecules of singlet oxygen produced per second per cm² from the surface of the plate using the RNO bleaching reaction. This method of generating ¹O₂ also seems promising for studying the killing of mammalian cells by ¹O₂ as the sole damaging species.