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Stern–Volmer kinetic relationships
This term applies broadly to variations of quantum yields of photophysical processes (e.g. fluorescence or phosphorescence ) or photochemical reactions (usually reaction quantum yield) with the concentration of a given reagent which may be a substrate or a quencher. In the simplest case, a plot of Math - ei (or Math - ei for emission) vs. concentration of quencher, Math - ei, is linear obeying the equation:
Math - e
In equation (1) Math - ei is referred to as the Stern–Volmer constant. Equation (1) applies when a quencher inhibits either a photochemical reaction or a photophysical process by a single reaction. Math - text and Math - text are the quantum yield and emission intensity radiant exitance, respectively, in the absence of the quencher Q, while Math - text and Math - text are the same quantities in the presence of the different concentrations of Q. In the case of dynamic quenching the constant Math - ei is the product of the true quenching constant Math - ei and the excited state lifetime, Math - text, in the absence of quencher. Math - text is the bimolecular reaction rate constant for the elementary reaction of the excited state with the particular quencher Q. Equation (1) can therefore be replaced by the expression (2):
Math - e
When an excited state undergoes a bimolecular reaction with rate constant Math - ei to form a product, a double-reciprocal relationship is observed according to the equation:
Math - e
where Math - ei is the quantum efficiency of product formation, Math - ei the efficiency of forming the reactive excited state, Math - ei the fraction of reactions of the excited state with substrate S which leads to product, and Math - ei is the concentration of reactive ground-state substrate. The intercept/slope ratio gives Math - ei. If Math - ei, and if a photophysical process is monitored, plots of equations (2) and (3) should provide independent determinations of the product-forming rate constant Math - text. When the lifetime of an excited state is observed as a function of the concentration of S or Q, a linear relationship should be observed according to the equation:
Math - e
where Math - text is the lifetime of the excited state in the absence of the quencher Q.
See also: self-quenching
Source:
PAC, 1996, 68, 2223 (Glossary of terms used in photochemistry (IUPAC Recommendations 1996)) on page 2277
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Cite as:
IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A.Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2008-10-07; version: 2.0.2.
DOI of this term: doi:10.1351/goldbook.S06004.
Original PDF version (may be out of date): http://www.iupac.org/goldbook/S06004.pdf.
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