Peters Baron
CECAM (Centre Européen de Calcul Atomique Moléculaire), Ecole Normale Supérieure, 46 Allée d'Italie, 69364 Lyon Cedex 7, France.
J Chem Phys. 2006 Dec 28;125(24):241101. doi: 10.1063/1.2409924.
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.
许多用于计算反应速率和自由能垒的方案都需要一个精确的反应坐标，但对于蛋白质折叠和成核等复杂过程，很难量化反应坐标的准确性。基于估计的反应概率的直方图检验，通常被用作良好反应坐标的定性指标。本文根据反应概率估计的直方图的均值和方差，推导出了本征反应概率分布的均值和方差。这些简便的公式使得首次对复杂系统的反应坐标误差进行定量计算成为可能。一个例子表明，伊辛模型中用于成核的彼得斯和特劳特反应坐标的近似过渡态表面给出的平均反应概率为0.495，标准差为0.042。
