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By Stephen G. Schulman

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Extra resources for Fluorescence and Phosphorescence Spectroscopy. Physicochemical Principles and Practice

Sample text

If a nonbonding pair on a solute molecule is bound by a hydrogen atom of the solvent, the hydrogen bonding interaction stabilizes the ground state as well as the η,π* state of the solute. However, because the ground state molecule has two electrons in the nonbonding orbital and the excited state has only one, the stabilization of the ground state is greatest. As a result, the energies of n ·*■ π* absorptions increase (the spectra shift to higher frequencies or shorter wavelengths) with increasing solvent hydrogen bond donor capacity.

In this chapter we shall consider the effects of solvent-solute and solute-solute interactions upon the properties of π -»- π*, n -* π* and intramolecular charge transfer transitions and the spectral bands they represent. 45 46 S. G. Schulman Solvent Effects on Electronic Spectra Solvent interactions with solute molecules are predominantly electrostatic and may be of the induced dipole-induced dipole, dipole-induced dipolef dipole-dipole or hydrogen bonding types (1). Additionally, hydrogen bonding usually accompanies dipole-dipole interaction as a mode of solvation.

G. Schulman is increased much more than φ and k , it is possible to populate the lowest triplet state efficiently, at the expense of the population of the lowest excited singlet state and still diminish the phosphorescence yield by introduction of a heteroatom or heavy atom. Thus, in many chelating ligands, coordination by very heavy ions such as Hg(II) and Tl(III) results in a decrease in both φ^ f and φp · Also, while benzene exhibits both fluorescence and phosphorescence, pyridine, having a nitrogen atom in the ring, exhibits neither· Delayed Fluorescence Occasionally, in rigid and viscous media, a second long lived emission band is observed in addition to the phosphorescence.

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