第八章 分子发光光谱法molecular_luminescence.ppt

Suda TGH （1）非辐射能量传递过程 （2）辐射能量传递过程 Emission and Excitation Spectra Characteristics of Fluorescence Spectrum Stokes Shift Mirror Symmetric Rule The excitation wavelength does not affect the shape of emission spectrum PHOSPHORESCENCE Variables That Affect Fluorescence Phosphorescence Quantum Yield Chemical Structure Environment Quantum Efficiency (?) i.e. the ratio of the number of molecules that luminesce to the total number of excited molecules. For a highly fluorescent molecule such as fluorescein, ??1 Chemical species that do not fluoresce appreciably have efficiencies that approach 0 Quantum Efficiency (?) It is determined by the relative rate constants for the processes by which the lowest excited singlet state is deactivated. Chemical Structure FLUORESCENCE AND STRUCTURE (CONTD.) FLUORESCENCE AND STRUCTURE (CONTD) FLUORESCENCE AND STRUCTURE (CONTD) HEAVY ATOM EFFECT HEAVY ATOM EFFECT STRUCTURAL RIGIDITY Environment Effects Effect of Solvent Effect of Temperature Effect of pH Effect of Dissolved Oxygen SOLVENT EFFECTS Effect of pH The fluorescence of an aromatic compound with acidic or basic ring substituents is usually pH-dependent. EFFECT OF CONCNETRATION ON FLUORESCENCE (briefly) EFFECT OF CONCENTRATION ON FLUORESCENCE (CONTD) EFFECT OF CONCENTRATION ON FLUORESCENCE (CONTD) Fluorescence Quenching Interaction with same analyte molecules or solvent molecules. Non-radiative emission. Dissolved oxygen: reduces the intensity of fluorescence due to photochemically induced oxidation of the fluorescing species. Instruments Components Sources Filters and monochromators Detectors Cells and cell compartments Sources A mercury or xenon arc lamp is commonly employed, which has a more intensity than those lamps used for absorption measurement. Lasers, particularly tunable dye laser, are also used for extremely high sensitivity. Cells and Cell Compartments Rectangular cells fabricated of silica Cell compartments must be designed to reduce scattered radiation reaching