For the field-free, spin-free linear rigid rotor in one fixed internal quantum state, the electric-dipole interaction is . A nonzero permanent electric dipole moment along the molecular axis allows pure rotational photon absorption with and photon emission with . The matrix element between initial and final quantum states must be nonzero: the existence of an energy gap alone is insufficient. Relative to a chosen axis, polarization of an electromagnetic wave along selects ; transverse polarization of an electromagnetic wave permits .[ref]
Lecture 24 Supplement: Energy levels of a Rigid Rotor by Dudley Herschbach. printed pp. 2–3: dipole transition integrals, polarization and selection rules
Hydrogen chloride and carbon monoxide are examples with a permanent electric dipole moment. By symmetry, molecular hydrogen and carbon dioxide have no permanent electric dipole moment in the ideal symmetric internal state. They still rotate and have rotational energy eigenvalues, but the simple permanent-electric dipole spectrum described here is absent. This restriction concerns this interaction and these assumptions, not every possible way of detecting molecular rotation.
Rigid rotor 2026-10-13
A rigid rotor models rotational motion with fixed internal separations. Its use in the synthetic Stark effect figure omits vibrational motion and additional interactions in real molecules.
Rigidity fixes the molecular geometry, not the orientation, and does not require a spherical mass distribution. Remove motion of the centre of mass, choose principal axes of the inertia tensor, and write the classical rotational kinetic energy asHere are the principal moments of inertia, components of angular velocity, and components of angular momentum. Quantization replaces these last components by angular momentum operators. Different principal moments of inertia produce different spectra: the single-constant linear rigid rotor is a special case, not a formula for every molecule.[ref]
Lecture 24 Supplement: Energy levels of a Rigid Rotor by Dudley Herschbach. printed p. 1: principal-axis energy and classification; pp. 4–5: asymmetric rotors