Freely jointed molecular chain: Dynamical variables, quantization, and statistical mechanics

Ramón F. Alvarez-Estrada
Phys. Rev. A 46, 3206 – Published 1 September 1992
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Abstract

A freely rotating linear chain, formed by N (N≥2) atoms with N-1 ‘‘bonds’’ of fixed lengths, is studied in three spatial dimensions. The classical (c) theory of that constrained system is formulated in terms of the classical transverse momentum -aj,c and angular momentum lj,c associated to the jth ‘‘bond’’ (j=1,...,N-1). The classical Poisson brackets of the Cartesian components of -aj,c and lj,c are shown to close an algebra. The quantization of the chain in spherical polar coordinates is carried out. The resulting ‘‘curved-space’’ quantization yields modified angular momenta lj. Quantum-mechanical transverse momenta (ej) are constructed. The commutators of the Cartesian components of ej and lj satisfy a closed Lie algebra, formally similar to the classical one for Poisson brackets. Using ej’s and lj’s, the quantum theory is shown to be consistent by itself and, via the correspondence principle, with the classical one. Several properties of ej and the modified lj are given: some sets of eigenfunctions (modified spherical harmonics, etc.) and uncertainty relations. As an example, the case of N=3 atoms in two spatial dimensions is worked out. The peculiar properties of the chain regarding distinguishability at the quantum level play an important role in justifying the absence of a ‘‘Boltzmann counting’’ factor [(N-1)!]1 in its classical statistical distribution. The physical limitations and the methodological virtues of the model at the classical and quantum levels, and its relationship to previous works by different authors, are discussed.

  • Received 20 April 1992

DOI:https://doi.org/10.1103/PhysRevA.46.3206

©1992 American Physical Society

Authors & Affiliations

Ramón F. Alvarez-Estrada

  • Departamento de Física Teórica, Facultad de Ciencias Físicas, Universidad Complutense de Madrid, 28040 Madrid, Spain

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Issue

Vol. 46, Iss. 6 — September 1992

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