Infrared Spectra of trans-nitrobis (2, 4-pentanediono) Aniline-Cobalt(III) Complexes

The infrared spectra of eighteen complexes of general formula trans-[Co(NO₂) (acac)₂ (R-C₆H₄NH₂)] (acac = acetylacetonate anion, R = 3- or 4-aniline substituent) are discussed. ¹⁵N-Labelling of the complexes containing aniline and p-toluidine yields assignments of the N-H, C-N and Co-N stretching frequencies and the N-H bending frequencies. These assignments receive support from the observed frequency shifts induced by varying the substituent R which also permits the assignment of the Co-o stretching frequencies.     

Line strength and halfwidth measurements from far infrared absorption spectra: Carbon monoxide

A method for deriving Lorentzian line shape parameters (line strengths and halfwidths) from absorption spectra taken at two different path lengths is discussed. Far i.r. absorption spectra of carbon monoxide are analysed to yield line strengths and halfwidths for the rotational transitions J″ = 3 through J>″ = 9. Experimental errors are discussed, and the value for the dipole moment derived from the line strengths, 0·108±0·005 D, is in agreement with the microwave value within experimental uncertainty. The Lorentzian halfwidths are compared, where appropriate, with two recent determinations of these quantities. Lorentzian halfwidths are also derived from absorption spectra taken at long path length using theoretical line strengths based upon μ_co = 0·112D.     

A momentum space view of the surface chemical bond

Well-ordered and oriented monolayers of conjugated organic molecules can offer new perspectives on surface bonding. We will demonstrate the importance of the momentum distribution, or symmetry, of the adsorbate molecules' π orbitals in relation to the states available for hybridization at the metal surface. Here, the electronic band structure of the first monolayer of sexiphenyl on Cu(110) has been examined in detail with angle-resolved ultraviolet photoemission spectroscopy over a large momentum range and will be compared to measurements of a multilayer thin film and to density functional calculations. In the monolayer, the one-dimensional intramolecular band structure can still be recognized, allowing an accurate determination of orbital modification upon bonding and the relative energetic positions of the electronic levels. It is seen that the character of the molecular π orbitals is largely maintained despite strong mixing between Cu and molecular states and that the lowest unoccupied molecular orbital (LUMO) is filled by hybridization with Cu s,p states rather than through a charge transfer process. It is also shown that the momentum distribution of the substrate states involved and the periodicity of the molecular overlayer play a large role in the final E(k) distribution of the hybrid states. The distinct momentum distribution of the LUMO, interacting with the Cu substrate s,p valence bands around the gap in the surface projection of the bulk band structure, make this system a particularly illustrative example of momentum resolved hybridization. This system demonstrates that, for hybridization to occur, not only do states require overlap in energy and space, but also in momentum.     

A HIGH RESOLUTION FLUORESCENCE DECAY AND DEPOLARIZATION STUDY OF HUMAN PLASMA APOLIPOPROTEINS

Abstract— Human plasma apolipoprotein A-I (apoA-I) and apolipoprotein C-I (apoC-I) were investigated by time-resolved fluorescence decay and depolarization. The tryptophyl fluorescence of apoA-I undergoes a double-exponential decay with lifetimes of 1.07 and 3.43 ns which remain unchanged over the range of apoA-I concentration studied.
The time-resolved fluorescence of both native and denatured forms of apoC-I exhibits an unusual tryptophyl fluorescence decay that was best fit to a triexponential function with lifetimes at 3.7 ± 0.2, 1.1 ± 0.1 and 0.1 ns at 2°C. The native and denatured forms of apoC-I had rotational correlation times of 1.42 and 1.19 ns at 20°C respectively. A shorter rotational correlation time associated with the internal tryptophan motions was not observed or resolved.
The decay of tryptophyl fluorescence in apoC-I/DPPC/cholesterol complex at 20°C is also triexponential with lifetimes at 4.94, 1.28 and 0.21 ns, which are longer than those of the uncomplexed forms. Two rotational correlation times of 28.32 and 0.59 ns at 20°C were resolved by fluorescence depolarization measurements. The long rotational time remained constant with temperatures above 30°C. Also, the temperature dependence of the order parameter, S², resembled a lipid phase transition curve with a transition midpoint at 38°C. The tryptophan and thus apoC-I are found to be affected by the bulk changes in the lipid.     

Pulse structure studies and absolute cavity length determination for a synchronously pumped picosecond dye laser

Second harmonic cross correlation functions of a pulse with its near neighbor have been studied in a synchronously pumped cw dye laser. Measurements were made both as a function of dye laser cavity length mismatch and the number of cavity round trips separating the correlated pulses. The pulse envelope is found to have a characteristic interpulse frequency determined by the pump laser, whereas the pulse substructure has a characteristic frequency determined by the dye laser cavity length. The cross correlation measurements allow experimental determination of the dye laser length corresponding to exact synchrony. In contrast to theoretical predictions the length of exact synchrony corresponds to optimum pulse shape and duration. Our results are discussed in terms of a simple model which leads to pulse duration estimates as much as twice those obtained by conventional analysis of autocorrelation traces.     

Reactivity of muonium atoms in aqueous solution

A beam of surface muons (4.1 MeV) was used to generate thermalised muonium atoms (μ⁺e^?) in aqueous solutions. From measurements of the muonium atom relaxation time in the presence of various solutes, bimolecular rate constants were determined and compared with the corresponding reactions of the much heavier isotope, the hydrogen atom.     

Anti-correlated spectral motion in bisphthalocyanines: evidence for vibrational modulation of electronic mixing

We exploit a coherently excited nuclear wave packet to study nuclear motion modulation of electronic structure in a metal bridged phthalocyanine dimer, lutetium bisphthalocyanine, which displays two visible absorption bands. We find that the nuclear coordinate influences the energies of the underlying exciton and charge resonance states as well as their interaction; the interplay of the various couplings creates unusual anti-correlated spectral motion in the two bands. Excited state relaxation dynamics are the same regardless of which transition is pumped, with decay time constants of 1.5 and 11 ps. The dynamics are analyzed using a three-state kinetic model after relaxation from one or two additional states faster than the experimental time resolution of 50-100 fs.     

Turning the [Ru(bpy)2dppz]2+ light-switch on and off with temperature

We report temperature-dependent excited-state lifetime measurements on [Ru(bpy)(2)dppz](2+) in both protic and aprotic solvents. These experiments yield a unifying picture of the excited-state photophysics that accounts for observations in both types of solvent. Our measurements support the notion of bpy-like and phz-like states associated with the dppz ligand and show that the ligand orbital associated with the bright state is similar in size to the corresponding orbital in the (3)MLCT state of [Ru(bpy)(3)](2+). In contrast to the current thinking, the experiments presented here indicate that the light-switch effect is not driven by a state reversal. Rather, they suggest that the dark state is always lowest in energy, even in aprotic solvents, and that the light-switch behavior is the result of a competition between energetic factors that favor the dark state and entropic factors that favor the bright (bpy) state.     

Further calculations on solubility of dipyrone in some binary solvent mixtures at various temperatures

The recently reported solubility data of dipyrone in binary solvent mixtures of {ethanol + water}, {methanol + ethanol} and {methanol + 1-propanol} at various temperatures have been used to report further numerical results based on the Jouyban–Acree model.     

The electronic structure of Fe1+xNb3-xSe10

Fe_1+xNb_3-xSe₁₀ has a crystal structure consisting of prismatic niobium chains and iron/niobium octahedral chains. A Charge Density Wave (CDW) has been observed at low temperatures, as might be expected from the similarity of the prismatic niobium chains to those present in NbSe₃. Here we report tight binding band structure calculations which indicate that the electrons responsible for conduction and the CDW reside primarily on the prismatic chains. The effects of disorder and stoichiometry in the iron/niobium octahedral chains on the electronic structure and CDW wave vector are discussed.