A combined explicit-implicit method for high accuracy reaction path integration.
We present the use of an optimal combined explicit-implicit method for following the reaction path to high accuracy. This is in contrast to most purely implicit reaction path integration algorithms, which are only efficient on stiff ordinary differential equations. The defining equation for the reaction path is considered to be stiff, however, we show here that the reaction path is not uniformly stiff and instead is only stiff near stationary points. The optimal algorithm developed in this work is a combination of explicit and implicit methods with a simple criterion to switch between the two. Using three different chemical reactions, we combine and compare three different integration methods: the implicit trapezoidal method, an explicit stabilized third order algorithm implemented in the code DUMKA3 and the traditional explicit fourth order Runge-Kutta method written in the code RKSUITE. The results for high accuracy show that when the implicit trapezoidal method is combined with either explicit method the number of energy and gradient calculations can potentially be reduced by almost a half compared with integrating either method alone. Finally, to explain the improvements of the combined method we expand on the concepts of stability and stiffness and relate them to the efficiency of integration methods.
Burger
Steven K
SK
Department of Chemistry, Duke University, Durham, North Carolina 27708-0346, USA.
Yang
Weitao
W
D000079:Acetaldehyde / Q000737:chemistry; D000438:Alcohols / Q000737:chemistry; D000465:Algorithms; D002627:Chemistry, Physical / Q000379:methods*; D003201:Computers; D008956:Models, Chemical; D015233:Models, Statistical; D008962:Models, Theoretical; D015203:Reproducibility of Results; D012821:Silanes / Q000737:chemistry; D012984:Software
D000438:Alcohols; D012821:Silanes; D000079:Acetaldehyde