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Introduction<br />

where np is the number <strong>of</strong> data points in the measured decay curve and Wj is<br />

a weighting factor. In the case <strong>of</strong> TCSPC methods, Wj follows Poisson statis-<br />

tics [44] .<br />

Because χ 2 depends on the number <strong>of</strong> data points (the larger the number <strong>of</strong> data<br />

points the larger the value <strong>of</strong> χ 2 ), the reduced form <strong>of</strong> χ 2 is used. In this case:<br />

χ 2 r = χ2<br />

n − p<br />

= χ2<br />

ν<br />

(1.18)<br />

For a good fit, the value <strong>of</strong> χ 2 r is expected to be close to unity. This is because each<br />

data point is expected to contribute to the deviation <strong>of</strong> χ 2 , which is normalised by<br />

the summation term in Equation 1.17. Another diagnostic for the goodness <strong>of</strong> fit is<br />

the autocorrelation function [45]. This is given by Equation 1.19 where Dk is the<br />

deviation in the k th data point and Dk+j is the deviation in the (k + j) th data point.<br />

AC(tj) =<br />

1 m<br />

m k=1 DkDk+j<br />

1 n<br />

n k=1 D2 k<br />

<br />

(1.19)<br />

Figure 1.15: Time domain intensity decay data for a dilute solution <strong>of</strong> HPTS dissolved<br />

in 0.2M phosphate buffer. Top: Time-resolved decay trace (blue) and IRF<br />

in red. The best fit to a mono-exponential decay function (black) is shown.<br />

The recovered residuals are given below. Bottom: The recovered autocorrelation<br />

function. λex = 405 nm, λem = 510 nm, τ = 5.4 ns, χ2 R = 1.01.<br />

A Poisson probability distribution is appropriate for counting experiments where the data represent<br />

the number <strong>of</strong> items or events observed per unit interval. For a Poisson distribution, the<br />

standard deviation is given by : σj = N(tj) where σj is the standard deviation <strong>of</strong> each data<br />

point, N(tj) is the measured data [47].<br />

28

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