The semiclassical initial value representation (SC-IVR) provides excellent tools for studying quantum dynamical effects of nuclear motion, including quantum coherences. One recent development in the SC-IVR is the concept of time-dependent sampling of the semiclassical integrand. The resulting sampling function of the initial phase space shows which initial conditions are most important to the calculation. When quantum coherences play a significant role, these initial distributions consist of distinct regions which give rise to interferences. This allows us to look for a smaller set of important 'quantum coherence collective variables,' analogous to the finding collective variables to represent free energy profiles as a subset of a higher dimensional space. This presentation will explore the interpretive, predictive, and practical uses of these initial distributions.

Important initial phase space distributions in semiclassical dynamics and the nature of quantum coherences

246th National Meeting (2013)

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