Inertial axis reorientation in the S 1←S 0 electronic transition of 2pyridone. A rotational Duschinsky effect. Structural and dynamical consequences J. Chem. Phys. 95, 8732 (1991); 10.1063/1.461209 Molecular dynamics study of rotational reorientation of tryptophan and several indoles in water J. Chem. Phys. 94, 3857 (1991); 10.1063/1.460661 The S 1-S 0 transition of indole and Ndeuterated indole: Spectroscopy and picosecond dynamics in the excited state J. Chem. Phys. 91, 6013 (1989); 10.1063/1.457418The rotationally resolved electronic spectrum of indole in the gas phase Rotationally resolved laser induced fluorescence excitation spectra of the S 1 ( 1 L b )←S 0 origin bands of indole, indazole, and benzimidazole have been measured. From these spectra, the rotational constants in both electronic states have been determined. The spectra of all three molecules exhibit ''anomalous'' rotational line intensities. These intensity perturbations are a result of the reorientation, upon electronic excitation, of the inertial axes of the molecule. Intensity analysis of the rotational lines yielded information about the inertial axis reorientation, and the direction of the transition moment vector for each molecule.
Indole and 3-methylindole (3-MI) doped into a polymethylmethacrylate (PMMA) film are studied by the Stark absorption (electroabsorption) spectroscopy. The 1La and 1Lb absorption bands are distinguished and the change in permanent dipole moment on 1La excitation is determined by a model fit to the measured absorption and electroabsorption spectra. Analysis of the spectra, measured at normal incidence and magic angle conditions, proved the essential role of the electric-field-induced orientation/alignment effects for polar indole and 3-MI molecules in the PMMA environment at room temperature.
In this study, we use the photosynthetic purple bacterium Rhodobacter sphaeroides to find out how the acclimation of photosynthetic apparatus to growth conditions influences the rates of energy migration toward the reaction center traps and the efficiency of charge separation at the reaction centers. To answer these questions we measured the spectral and picosecond kinetic fluorescence responses as a function of excitation intensity in membranes prepared from cells grown under different illumination conditions. A kinetic model analysis yielded the microscopic rate constants that characterize the energy transfer and trapping inside the photosynthetic unit as well as the dependence of exciton trapping efficiency on the ratio of the peripheral LH2 and core LH1 antenna complexes, and on the wavelength of the excitation light. A high quantum efficiency of trapping over 80% was observed in most cases, which decreased toward shorter excitation wavelengths within the near infrared absorption band. At a fixed excitation wavelength the efficiency declines with the LH2/LH1 ratio. From the perspective of the ecological habitat of the bacteria the higher population of peripheral antenna facilitates growth under dim light even though the energy trapping is slower in low light adapted membranes. The similar values for the trapping efficiencies in all samples imply a robust photosynthetic apparatus that functions effectively at a variety of light intensities.
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