title: Observation time scale, free-energy landscapes, and molecular symmetry.
abstract: When structures that interconvert on a given time scale are lumped together, the corresponding free-energy surface becomes a function of the observation time. This view is equivalent to grouping structures that are connected by free-energy barriers below a certain threshold. We illustrate this time dependence for some benchmark systems, namely atomic clusters and alanine dipeptide, highlighting the connections to broken ergodicity, local equilibrium, and "feasible" symmetry operations of the molecular Hamiltonian.
authors.affiliation: University Chemical Laboratories, Cambridge CB2 1EW, United Kingdom.
authors.forename: David J
authors.initials: DJ
authors.lastname: Wales
authors.forename: Peter
authors.initials: P
authors.lastname: Salamon
mesh_terms: D000409:Alanine / Q000737:chemistry; D008956:Models, Chemical; D011789:Quantum Theory; D013816:Thermodynamics; D013997:Time Factors
chemical_list: D000409:Alanine