Mo/ller operators in the formulation of reaction probabilities in terms of wave packet correlation functions allow us to define the wave packets in the interaction region rather than in the asymptotic region of the potential surface. We combine Mo/ller operators with the semiclassical propagator of Herman and Kluk. This does not involve further approximations and can be used with any initial value representation (IVR) semiclassical propagator. Time propagation in asymptotic regions of the potential due to Mo/ller operators reduces the oscillations of the propagator integrand and improves convergence of the results with respect to the number of trajectories. The effectiveness of Mo/ller operators for semiclassical reaction probability calculation is demonstrated for the collinear hydrogen exchange reaction. Full convergence is achieved and the number of classical trajectories is reduced by a factor of 10 compared to the calculation without Mo/ller operators.
Published in The Journal of Chemical Physics, Volume 114, Issue 1060, 2001.
Copyright 2001 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
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Garashchuk, S. & Light, J. C. (2001). Semiclassical application of the Mo/ller operators in reactive scattering. The Journal of Chemical Physics, 114, 1060. http://dx.doi.org/10.1063/1.1333408
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