Efficient path sampling on multiple reaction channels

Due to the time scale problem, rare events are not accessible by straight forward molecular dynamics. The presence of multiple reaction channels complicates the problem even further. The feasibility of the standard free energy based methods relies strongly on the success in finding a proper reaction coordinate. This can be very difficult task in high-dimensional complex systems and even more if several distinct reaction channels exist. Moreover, even if a proper reaction coordinate can be found, ergodic sampling will be a challenge. In this article, we discuss the recent advancements of path sampling methods to tackle this problem. We argue why the path sampling methods, via the transition interface sampling technique, is less sensitive to the choice of reaction coordinate. Moreover, we review a new algorithm, parallel path swapping, that can dramatically improve the ergodic sampling of trajectories for the multiple reaction channel systems.Comment: 7 pages, 4 figures. Article submitted for the proceedings of the Conference on Computational Physics, Brussels 200

Contact structures of arbitrary codimension and idempotents in the Heisenberg algebra

A contact manifold is a manifold equipped with a distribution of codimension one that satisfies a `maximal non-integrability' condition. A standard example of a contact structure is a strictly pseudoconvex CR manifold, and operators of analytic interest are the tangential Cauchy-Riemann operator and the Szego projector onto its kernel. The Heisenberg calculus is the natural pseudodifferential calculus developed originally for the analysis of these operators. We introduce a `non-integrability' condition for a distribution of arbitrary codimension that directly generalizes the definition of a contact structure. We call such distributions polycontact structures. We prove that the polycontact condition is equivalent to the existence of generalized Szego projections in the Heisenberg calculus, and explore geometrically interesting examples of polycontact structures.Comment: 13 pages. Second version contains major revisio

The Geometry of the Osculating Nilpotent Group Structures of the Heisenberg Calculus

We explore the geometry that underlies the osculating nilpotent group structures of the Heisenberg calculus. For a smooth manifold $M$ with a distribution $H\subseteq TM$ analysts use explicit (and rather complicated) coordinate formulas to define the nilpotent groups that are central to the calculus. Our aim in this paper is to provide insight in the intrinsic geometry that underlies these coordinate formulas. First, we introduce `parabolic arrows' as a generalization of tangent vectors. The definition of parabolic arrows involves a mix of first and second order derivatives. Parabolic arrows can be composed, and the group of parabolic arrows can be identified with the nilpotent groups of the (generalized) Heisenberg calculus. Secondly, we formulate a notion of exponential map for the fiber bundle of parabolic arrows, and show how it explains the coordinate formulas of osculating structures found in the literature on the Heisenberg calculus. The result is a conceptual simplification and unification of the treatment of the Heisenberg calculus.Comment: Some parts rewritten; section 3 added. 33 page