Statistics and Nos\'e formalism for Ehrenfest dynamics

Quantum dynamics (i.e., the Schr\"odinger equation) and classical dynamics (i.e., Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. In this paper we first show that the hybrid quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well defined Poisson bracket allows to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. Once we know the canonical distribution of a Ehrenfest system, it is straightforward to extend the formalism of Nos\'e (invented to do constant temperature Molecular Dynamics by a non-stochastic method) to our Ehrenfest formalism. This work also provides the basis for extending stochastic methods to Ehrenfest dynamics.Comment: 28 pages, 1 figure. Published version. arXiv admin note: substantial text overlap with arXiv:1010.149

Exploration of Reaction Pathways and Chemical Transformation Networks

For the investigation of chemical reaction networks, the identification of all relevant intermediates and elementary reactions is mandatory. Many algorithmic approaches exist that perform explorations efficiently and automatedly. These approaches differ in their application range, the level of completeness of the exploration, as well as the amount of heuristics and human intervention required. Here, we describe and compare the different approaches based on these criteria. Future directions leveraging the strengths of chemical heuristics, human interaction, and physical rigor are discussed.Comment: 48 pages, 4 figure

Fluctuations in Nonequilibrium Statistical Mechanics: Models, Mathematical Theory, Physical Mechanisms

The fluctuations in nonequilibrium systems are under intense theoretical and experimental investigation. Topical ``fluctuation relations'' describe symmetries of the statistical properties of certain observables, in a variety of models and phenomena. They have been derived in deterministic and, later, in stochastic frameworks. Other results first obtained for stochastic processes, and later considered in deterministic dynamics, describe the temporal evolution of fluctuations. The field has grown beyond expectation: research works and different perspectives are proposed at an ever faster pace. Indeed, understanding fluctuations is important for the emerging theory of nonequilibrium phenomena, as well as for applications, such as those of nanotechnological and biophysical interest. However, the links among the different approaches and the limitations of these approaches are not fully understood. We focus on these issues, providing: a) analysis of the theoretical models; b) discussion of the rigorous mathematical results; c) identification of the physical mechanisms underlying the validity of the theoretical predictions, for a wide range of phenomena.Comment: 44 pages, 2 figures. To appear in Nonlinearity (2007