Rotational energy surfaces and high-J eigenvalue structure of polyatomic molecules

1984/05/01 by William G. Harter, Chris W. Patterson · 1 voice
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Molecular Spectroscopy and Structure #Molecular spectroscopy and chirality

paper · doi:10.1063/1.447255

openalex publication_date 1984/05/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/06/11

Abstract

A rotational analog of the vibrational potential energy surface is introduced for describing the rotational fine structure of polyatomic molecules. Classical trajectories on rotational energy (RE) surfaces are related to quantum rotational eigenvalue structure. Interpretation of RE surfaces shows how very different types of molecules may undergo dynamical symmetry breaking and a corresponding clustering of rotational energy sublevels for high angular momentum (J>10). Cluster splitting and spacing are calculated using semiclassical quantization methods. Some consequences of dynamical symmetry breaking such as mixing of nuclear spin species are discussed qualitatively.

Discussions

• Imagine an elliptical region of phase space $\{(q,p)\in \mathbb{R}^2:p^2/2m + kq^2/2=E\}$ of constant energy $E$ for a 1D harmonic oscillator. Since all points on the ellipse have the same energy, the [stackexchange, 5 points]

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