By J. N. Demas
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Extra resources for Excited State Lifetime Measurements
Sample text
For demonstration purposes we develop the Stern-Volmer equation using a steady state analysis. Under conditions of steady illumination [*D] in Eq. ,
MEAN LIFE AND HALF-LIFE The half-life Tm is a pragmatic quantity defined as the time it takes the concentration to fall to half its original value. In excited state measurements this usually means the time required for the emission intensity to decrease by half. Although Tm is easy to read from oscilloscope traces, it is of limited theoretical significance. A more fundamental quantity is the mean lifetime r which is sometimes also denoted by r m . For an exponential decay, we shall show that r = \lk (3-6) The initial [*D], [*D]0, is reduced by a factor of lie at / = r.
As shown later, discrepancies between the φ and τ Stern-Volmer plots can supply useful chemical information. Equation (3-20b) can be used to evaluate k2 directly; see Fig. 3-4. Until the development of computerized data acquisition systems with on-line data reduction capabilities, this approach was generally unattractive be- 38 3. SIMPLE SYSTEMS [ptciV] x ICT ( M ) Fig. 3-2. Quenching of the emission of Ru(bipy)3Cl2 in deoxygenated 1 x 10~3 M HC104 by PtClJ". 685 usec); O and D, relative intensity data taken before and after the lifetime measurements, respectively.