Models of macromolecular chains based on Classical and Quantum Mechanics: comparison with Gaussian models

Abstract

Different approaches to the study of open linear freely-jointed (unhindered) threedimensional macromolecular chains at thermal equilibrium, based upon either Classical Hamiltonian Dynamics with constraints (namely, a formulation equivalent to Kramers' one) or Quantum Mechanics (with stiff harmonic springs), are reviewed and discussed in detail. Results from those approaches are compared to those arising from the standard Gaussian model. Fraenkel's approach, based upon Classical Mechanics (with stiff harmonic springs) and its comparison with the Gaussian model are also treated. It is argued that the quantum formulation is required in order that the treatment of the high-frequency vibrations be consistent. The role of the uncertainty principle is discussed, in support of the quantum-mechanical approach. At a later stage, internal rotations can be treated through Classical Statistical mechanics, under certain conditions. The quantum-Mechanics-based model appears to be consistent with the Gaussian model, while the one based upon constrained Hamiltonian Dynamics yields certain discrepancies with the latter. Classical and quantum-mechanical approaches to open linear freely-rotating (hindered) threedimensional macromolecular chains are also treated: the consistency of the quantum-mechanics-based model is displayed by deriving approximately the existence of a persistence length. It is argued that the possible advantages of the quantum-mechanical formulation should be expected not at large scales but at shorter ones. The specific topics to be treated are described in the summary of contents given below.