Augmented Harmonic Linear Discriminant Analysis

Abstract

Many processes of scientific and technological interest are characterized by time scales that render their simulation impossible if one uses present day simulation capabilities. To overcome this challenge a variety of enhanced simulation methods has been developed. A much-used class of methods relies on the use of collective variables. The efficiency of these methods relies critically on an educated guess of the collective variables. For this reason much effort has been devoted to the construction and improvement of collective variables. Among the many methods proposed, harmonic linear discriminant analysis has proven effective. This method builds the collective coordinates solely from the knowledge of the fluctuations in the different metastable state. In this Letter we propose to improve upon the harmonic linear discriminant analysis by adding to the construction of the collective coordinates an extra bit of information, namely that of the transition state ensemble. Configurations belonging to the transition state ensemble are harnessed by the use of the spring shooting transition path sampling algorithm. We show on a challenging example that these coordinates thus augmented not only perform better in the calculation of the static properties, but also accelerate considerably the calculation of reaction rates.