Using the histogram test to quantify reaction coordinate error.
Many schemes for calculating reaction rates and free energy barriers require an accurate reaction coordinate, but it is difficult to quantify reaction coordinate accuracy for complex processes like protein folding and nucleation. The histogram test, based on estimated committor probabilities, is often used as a qualitative indicator for good reaction coordinates. This paper derives the mean and variance of the intrinsic committor distribution in terms of the mean and variance of the histogram of committor estimates. These convenient formulas enable the first quantitative calculations of reaction coordinate error for complex systems. An example shows that the approximate transition state surface from Peters' and Trout's reaction coordinate for nucleation in the Ising model gives a mean committor probability of 0.495 and a standard deviation of 0.042.
Peters
Baron
B
CECAM (Centre Européen de Calcul Atomique Moléculaire), Ecole Normale Supérieure, 46 Allée d'Italie, 69364 Lyon Cedex 7, France. bpeters@cecam.org