Quantum chemical simulation of excited states of chlorophylls, bacteriochlorophylls and their complexes

The present review describes the use of quantum chemical methods in estimation of structures and electronic transition energies of photosynthetic pigments in vacuum, in solution and imbedded in proteins. Monomeric Mg-porphyrins, chlorophylls and bacteriochlorophylls and their solvent 1:1 and 1:2 complexes were studied. Calculations were performed for Mg-porphyrin, Mg-chlorin, Mg-bacteriochlorin, mesochlorophyll a, chlorophylls a, b, c(1), c(2), c(3), d and bacteriochlorophylls a, b, c, d, e, f, g, h, plus several homologues. Geometries were optimised with PM3, PM3/CISD, PM5, ab initio HF (6-31G*/6-311G**) and density functional B3LYP (6-31G*/6-311G**) methods. Spectroscopic transition energies were calculated with ZINDO/S CIS, PM3 CIS, PM3 CISD, ab initio CIS, time-dependent HF and time-dependent B3LYP methods. Estimates for experimental transition energies were obtained from linear correlations of the calculated transition energies of 1:1 solvent complexes against experimentally recorded solution energies (scaling). According to the calculations in five-coordinated solvent complexes the magnesium atom lies out of the porphyrin plane, while in six-coordinated complexes the porphyrin is nearly planar. Charge densities on magnesium and nitrogen atoms were strongly dependent on the computational method deployed. Several dark states of low oscillator strength below the main Soret band were predicted for solvent complexes and chlorophylls and bacteriochlorophylls in protein environment. Such states, though not yet identified experimentally, might serve as intermediate states for excitation energy transfer in photosynthetic complexes. Q(y), Q(x) and Soret transition energies were found to depend on the orientation of the acetyl group and external pressure. A method to estimate site energies and dimeric interaction energies and to simulate absorption and CD spectra of photosynthetic complexes is described. Simulations for the light harvesting complexes Rhodospirillum molischianum, chlorosomes of Chlorobium tepidum and Chloroflexus aurantiacus, and LHC-II of Spinacia oleracea are presented as examples.     

Influence of ligand structure on the stability and oxidation of copper nanoparticles

The stability and oxidation of copper nanoparticles stabilized with various ligands have been studied. Lauric acid-capped copper nanoparticles were prepared by a modified Brust-Schiffrin method. Then, ligand exchange with an excess of different capping agents was performed. Oxidation and stability were studied by UV-vis, XRD, and TEM. Alkanethiols and oleic acid were found to improve air stability. The oxidation resistance of thiol-capped copper nanoparticles was found to increase with the chain length of the thiol. However, excess thiol caused etching of the particles under nitrogen. With oleic acid no etching was observed under nitrogen. After oxidation, no traces of the ligand-exchanged particles were found, suggesting their dissolution due to excess ligand. Oleic acid protected the particles against oxidation better than the tested thiols at large excess (ligand-copper ratio 20:1).     

Green functions in stochastic field theory

Functional representations are reviewed for the generating function of Green functions of stochastic problems stated either with the use of the Fokker-Planck equation or the master equation. Both cases are treated in a unified manner based on the operator approach similar to quantum mechanics. Solution of a second-order stochastic differential equation in the framework of stochastic field theory is constructed. Ambiguities in the mathematical formulation of stochastic field theory are discussed. The Schwinger-Keldysh representation is constructed for the Green functions of the stochastic field theory which yields a functional-integral representation with local action but without the explicit functional Jacobi determinant or ghost fields.     

Standoff alpha radiation detection for hot cell imaging and crime scene investigation

Optical Review - This paper presents the remote detection of alpha contamination in a nuclear facility. Alpha-active material in a shielded nuclear radiation containment chamber has been localized...     

Estimating a linear functional relationship under linear constraints for errors

Maximum likelihood estimates for parameters in a linear functional relationship are derived when the errors are also linearly related for each observation. This is approximately the case, for example, when both variables are smooth functions of time and their values are recorded as an experimental unit reaches a certain state. This kind of model specification was needed to describe how the timing of growth cessation of trees depends on night length and temperature sum. If the slope in the constraint equation for errors varies, then an iterative estimation procedure is needed. The estimation method is extended for a two-phase linear model.     

Pointwise Hardy inequalities and uniformly fat sets

We prove that it is equivalent for domain in to admit the pointwise -Hardy inequality, have uniformly -fat complement, or satisfy a uniform inner boundary density condition.

     

High-energy sub-nanosecond optical pulse generation with a semiconductor laser diode for pulsed TOF laser ranging utilizing the single photon detection approach

Bulk and quantum well laser diodes with a large equivalent spot size of d _a /Γ _a  ≈ 3 µm and stripe width/cavity length of 30 µm/3 mm were realized and tested. They achieved a pulse energy and pulse length of the order of ~1 nJ and ~100 ps, respectively, with a peak pulse current of 6–8 A and a current pulse width of 1 ns. The 2D characteristics of the optical output power versus wavelength and time were also analyzed with a monochromator/streak camera set-up. The far-field characteristics were studied with respect to the time-homogeneity and energy distribution. The feasibility of a laser diode with a large equivalent spot size in single photon detection based laser ranging was demonstrated to a non-cooperative target at a distance of a few tens of meters.     

Excitation energy transfer in isolated chlorosomes from Chlorobaculum tepidum and Prosthecochloris aestuarii

Excitation energy transfer in chlorosomes from photosynthetic green sulfur bacteria, Chlorobaculum (Cba.) tepidum and Prosthecochloris (Pst.) aestuarii, have been studied at room temperature by time-resolved femtosecond transient absorption spectroscopy. Bleach rise times from 117 to 270 fs resolved for both chlorosomes reflect extremely efficient intrachlorosomal energy transfer. Bleach relaxation times, from 1 to 3 ps and 25 to 35 ps, probed at 758 nm were tentatively assigned to intrachlorosomal energy transfer based on amplitude changes of the global fits and model calculations. The anisotropy decay constant of about 1 ps resolved at 807 nm probe wavelength for the chlorosomes from Chloroflexus aurantiacus, Pst. aestuarii and Cba. tepidum was related to energy transfer between bacteriochlorophyll a molecules of the baseplate and partly to intrachlorosomal energy transfer. The longer anisotropy components 6.6, 8.8 and 12.1 ps resolved for the three chlorosomes, respectively, were assigned to chlorosome to baseplate energy transfer. Global fits of magic-angle data also revealed longer chlorosome to baseplate energy transfer components from 95 to 135 ps, in accord with results from simulations.