Pure rotational electric-dipole selection rules

ID: pure-rotational-electric-dipole-selection-rules

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]
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.

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