 Cycle-gain uncertainty

Cycle-gain uncertainty describes uncertainty in the product of the multipliers achieved over repeated chemical multiplication reaction cycles. Its size depends on cycle-gain correlation: environmental or reagent effects shared across cycles behave differently from independent cycle variation.

For positive multipliers $K_j$, write $G={\prod }_{j=1}^n{K}_j$ and ${\ell }_j=\ln K_j$. Then $\ln G={\sum }_j{\ell }_j$, soFor small relative errors, $u(G)/G$ is approximately the standard deviation of $\ln G$. This applies the correlated-input uncertainty propagation framework to the product model.^[ref]

An original intermediate-correlation model sets $\mathrm{Cov}({\ell }_i,{\ell }_j)={\sigma }^2{\rho }^{|i-j|}$. Grouping equal separations givesFor $n=4$, $\sigma =0.02$ and $\rho =0.5$, the bracket is8.25, giving relative standard uncertainty approximately0.0574. Independent cycles would give0.040, while completely shared log-error would give0.080. Specifying only the uncertainty of each individual cycle leaves total-gain uncertainty undetermined.

If the log-multipliers are jointly normally distributed, $G$ has a log-normal distribution. With ${\mu }_G=E(\ln G)$,These exact relations under the stipulated distribution distinguish the mean gain from its median when variation is substantial.

Estimate correlations from a justified shared-input model or appropriately replicated sequences. Common calibration, reagent variation and cycle-dependent depletion may contribute. Adding more ideal cycles can increase nominal gain while making the final measurement uncertainty more sensitive to those shared inputs.