LOW-TEMPERATURE PHOTCOXIDATION OF CHLOROPHYLL-A*

Abstract— Illumination of chlorophyll at low temperature, in solvents containing organic Lewis bases and oxygen, leads to oxidation of the C-2 vinyl group. This oxidation proceeds through a series of thermal and photochemical changes, including initial formation of a new compound (I) absorbing at 620 nm. This undergoes further rapid photochemical (or thermal) conversion back to a chlorin-like substance (II), and much slower phototransformation to a third intermediate (III) absorbing near 500 nm. The reaction requires complexed metal (Mg or Zn), but not an intact cyclopentanone ring. The ‘620’ photoproduct is assigned to a cyclic peroxide involving C-1 of chlorophyll and the vinyl group.     

EFFECTS OF STEADY ANGLE OF ATTACK ON NONLINEAR GUST RESPONSE OF A DELTA WING MODEL

The effects of a steady angle of attack on the nonlinear aeroelastic response of a delta wing model to a periodic gust have been studied. For the theoretical analysis, a three-dimensional time-domain vortex lattice aerodynamic model and a reduced order aerodynamic technique were used and the structure was modelled using von Karman plate theory that allows for geometric strain–displacement nonlinearities in the delta wing structure. Also, an experimental investigation has been carried out in the Duke wind tunnel using a rotating slotted cylinder gust generator and an Ometron VPI 4000 Scanning Laser Vibrometer measurement system to measure deflections (velocities) of a delta wing test model. The fair to good quantitative agreement between theory and experiment verifies that the present analytical approach has reasonable accuracy and good computational efficiency for nonlinear gust response analysis in the time-domain. The results also contribute to a better physical understanding of the nonlinear aeroelastic response of a delta wing model to gust loads when the steady angle of attack is varied.     

The thymine radicals and their respective anions: molecular structures and electron affinities

The adiabatic electron affinities (AEA), vertical electron affinities (VEA) and vertical detachment energies (VDE) are predicted for six different radicals derived from thymine by the removal of one hydrogen atom. Geometry optimizations were carried out utilizing the DFT functionals B3LYP, BLYP and BP86 with double-c quality basis sets plus polarization and diffuse functions (DZP++). These methods have been carefully calibrated for the prediction of electron affinities [RIENSTRA-KIRACOFE, J. C., TSCHUMPER, G. S., SCHAEFER, H. F., NANDI, S., and ELLISON, G. B., 2002, Chem. Rev., 102, 231]. All optimized structures were confirmed to be minima via vibrational frequency analyses. Both the neutrals and the anion radicals were observed to possess C_s, symmetry, conserving the parent molecule's qualitative conformation. The electron affinities ranged between 1.04 and 3.74eV for the different radicals, contrasting to the small electron affinities associated with the closed-shell thymine species. The radicals with a hydrogen atom removed from one of the nitrogens present the largest electron affinities of all six radicals investigated (3.22eV for NI and 3.74eV for N3).     

Solution of Wiener-Hopf Integral Equations using the Fast Fourier Transform

The Wiener-Hopf method of solving the linear integral equation can be carried out conveniently and efficiently using the FastFourier Transform. Given the values of h(t) and g(t) at equidistantpoints along the t-axis, the solution f(t) is obtained by dintof seven Fourier transforms.     

Electron affinities of cyano-substituted ethylenes

Electron affinities of ethylene and six cyano-substituted ethylenes (cyanoethylene, 1, 1-dicyanoethylene, cis-1, 2-dicyanoethylene, trans-1, 2-dicyanothylene, tricyanoethylene, and tetracyanoethylene) were determined using six different density functional or hybrid Hartree-Fock/density functional methods. Equilibrium geometries and harmonic vibrational frequencies for each species were determined with each density functional method. Experimental electron affinities exist for three of the six systems studied (cyanoethylene, trans-1, 2-dicyanoethylene, and tetracyanoethylene); for the three systems, the absolute average EA errors for the different methods are 0.10eV (BLYP), 0.19ev (BHLYP), 0.22eV (B3LYP), 0.20eV (BP86), 0.78eV (B3P86), and 0.81eV (LSDA). The electron affinities of gem-dicyanoethylene, cis-discyanoethylene, and tricyanoethylene are not known from experiment but are predicted here to be 1.23eV (gem-dicyanoethylene), 1.32eV (cis-dicyanoethylene), and 2.41eV (tricyanoethylene). Contrary to earlier suggestions, tetracyanoethylene is predicted to be planar, rather than twisted. Density functional theory predicts that the ²B_1u state of the ethylene anion lies lower than the ²B_2g state, which is reported by experimentalists as the (transient) ground state, and lower than the ²A_g state. Coupled-cluster results indicate that the ²A_g state is lower than either the ²B_2g or ²B_1u states. The energetic stabilization of cyano substitution on ethylene results from the π and π? conjugation of multiple cyano groups. The HOMO-LUMO gap in ethylene decreases with increasing cyano substitution, from 7.2eV in C₂H₄ to 3.8eV in C₂(CN)₄, explaining the extreme difference between the electron affinities of ethylene (negative) and tetracyanoethylene (～T3.0eV).     

Characterization of the [Xtilde] 1Σ+ à 3Π and à 1Π electronic states of BBO

The three lowest-lying electronic states, [Xtilde] ¹Σ⁺, à ³II and à ¹II, of the linear BBO molecule have been systematically investigated using ab initio electronic structure theory. The equilibrium structures and physical properties including dipole moments, vibrational frequencies and associated infrared intensities, Renner parameters and energetics for the three states of BBO have been determined employing SCF, CISD, CCSD and CCSD(T) levels of theory and a wide range of basis sets. The ground state of BBO presents a degenerate real bending frequency, while the à ³II and à ¹II states show two distinct real bending frequencies due to the Renner-Teller interaction. The bending motion of the à ¹II state was analysed using the equation-of-motion (EOM)-CCSD and EOM-CC3 techniques in order to avoid possible variational collapse to a lower-lying state. The [Xtilde] ¹Σ⁺-à ³II separation was predicted to be T ₀ = 16.6 kcal mol^?1 (5800 cm^?1, 0.719 eV) at the cc-pVQZ CCSD(T) level of theory. With the cc-pVQZ EOM-CC3 method the [Xtilde] ¹Σ⁺-à ¹II splitting was predicted to be T ₀ = 48.0 kcal mol^?1 (16 800 cm^?1, 2.08 eV), which is in good agreement with the experimental value of T ⁰ = 46.6 kcal mol^?1 (16 300 cm^?1, 2.02 eV). The Renner parameters and averaged harmonic frequencies of the bending mode were determined to be ? = 0.184 and ω₂ = 363 cm^?1 for the à ³II state, and ? = 0.246 and ω₂ = 383cm^?1 for the à ¹II state. The theoretical [Xtilde] ¹Σ⁺ state harmonic B-B stretching frequency ω₃ = 636 cm^?1 is somewhat higher than the experimental estimate of 582 cm^?1 and the predicted à ¹II state harmonic B-B stretching frequency ω₃ = 861 cm^?1 is significantly higher than the experimental estimate of 440 cm^?1     

THE CHEMILUMINESCENCE OF INDOLE DERIVATIVES IN DIMETHYL SULFOXIDE*

The chemiluminescent autoxidation of over fifty indoles has been measured in dimethyl sulfoxide (DMSO). The 3-alkylindole derivatives represent the brightest and most efficient members of this group. The chemiluminescence yield (per mole) of skatole is (1·5 ± 0·6) × 10^-3. The chemiluminescence spectrum of skatole is identical with the fluorescence spectrum of o-formamidoacetophenone in the same environment Similar results for 2,3-dimethylindole lead to the identification of the acylamide anion as the emitter in indole chemiluminescence. A peroxide ring cleavage excitation mechanism is proposed.     

III: PROPERTIES OF COMPLEX SYSTEMS

The molecular structures, vibrational frequencies, dissociation energies and electron affinities of the Br₂/Br^? ₂, Br₂O/Br₂O^?, Br₂O₂/Br₂O^? ₂, Br₂O₃/Br₂O^? ₃, and Br₂O₄/Br₂O^? ₄ systems have been investigated using density functional theory (DFT) and hybrid Hartree-Fock/density functional theory. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities, (Rienstra-Kiracofe, J. C., Tschumper, G. S., Shaefer, H. F., Nandi, S. and Ellison, G. B., 2002, Chem. Rev., 102, 231). Four different types of neutral/anion energetic difference are reported in this work: the adiabatic electron affinity (EA_ad), the zero-point corrected EA_ad (EA_zero), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The basis set used in this work is of double-zeta plus polarization quality with additional s- and p-type diffuse functions, and is denoted as DZP⁺⁺. The BHLYP method does well in reproducing the very limited experimental energetics, while the B3LYP method does well for the few known vibrational frequencies. The final predicted electron affinities with the BHLYP method are 3.41 eV (Br, experiment 3.36 eV), 3.02 eV (Br₂, experiment 2.6 ± 0.2 eV), 3.27 eV (Br₂O), 2.93 eV (Br₂O₂), 3.07 eV (Br₂O₃), and 2.54 eV (Br₂O₄). The global minimum structures for several of the larger dibromine oxides and their anions are unusual. For neutral Br₂O₂ the peroxide structure (BrOOBr) lies lowest, but for the anion a loosely bound C_s symmetry BrO-BrO^? structure lies lowest for the hybrid functionals, while a C₂ symmetry peroxide BrOOBr^? structure lies lowest for the pure functionals. Furthermore, the C₂ structures are found to exhibit an inverse symmetry breaking problem, and should be interpreted with caution. For neutral Br₂O₃, a chain structure Br-O₃-Br lies lowest, while the complex Br···O₃···Br^? lies lowest for the negative ion. For neutral Br₂O₄, a chain structure Br-O₄-Br lies lowest, while the complex BrO^?···BrO₃ lies lowest for the negative ion.