Hot band

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In molecular vibrational spectroscopy, a hot band (or hot transition) is a transition between two states of a single normal mode of vibration, neither of which is the overall ground state. In infrared or Raman spectroscopy, hot bands refer to those transitions for a particular vibrational mode which arise from a state containing thermal population of another vibrational mode. For example, for a molecule with 3 normal modes, <math>nu_1</math>, <math>nu_2</math> and <math>nu_3</math>, the transition <math>101</math> ← <math> 001</math>, would be a hot band, since the initial state has one quantum of excitation in the <math>nu_3</math> mode. Hot bands are distinct from combination band, which involve simultaneous excitation of multiple normal modes with a single photon, and overtones, which are transitions that involve changing the vibrational quantum number for a normal mode by more than 1.

Vibrational hot bands

In the harmonic approximation, the normal modes of a molecule are not coupled, and all vibrational quantum levels are equally spaced, so hot bands would not be distinguishable from so-called "fundamental" transitions arising from the overall vibrational ground state. However, vibrations of real molecules always have some anharmonicity, which causes coupling between...
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