Polarization at high frequencies
المؤلف:
Peter Atkins، Julio de Paula
المصدر:
ATKINS PHYSICAL CHEMISTRY
الجزء والصفحة:
626
2025-12-15
39
Polarization at high frequencies
When the applied field changes direction slowly, the permanent dipole moment has time to reorientate—the whole molecule rotates into a new direction—and follow the field. However, when the frequency of the field is high, a molecule cannot change direction fast enough to follow the change in direction of the applied field and the dipole moment then makes no contribution to the polarization of the sample. Because a molecule takes about 1 ps to turn through about 1 radian in a fluid, the loss of this contribution to the polarization occurs when measurements are made at frequencies greater than about 1011 Hz (in the microwave region). We say that the orientation polarization, the polarization arising from the permanent dipole moments, is lost at such high frequencies.
The next contribution to the polarization to be lost as the frequency is raised is the distortion polarization, the polarization that arises from the distortion of the positions of the nuclei by the applied field. The molecule is bent and stretched by the applied field, and the molecular dipole moment changes accordingly. The time taken for a molecule to bend is approximately the inverse of the molecular vibrational frequency, so the distortion polarization disappears when the frequency of the radiation is increased through the infrared. The disappearance of polarization occurs in stages: as shown in the Justification below, each successive stage occurs as the incident frequency rises above the frequency of a particular mode of vibration. At even higher frequencies, in the visible region, only the electrons are mobile enough to respond to the rapidly changing direction of the applied field. The polarization that remains is now due entirely to the distortion of the electron distribution, and the surviving contribution to the molecular polarizability is called the electronic polarizability.
Justification 18.3 The frequency-dependence of polarizabilities The quantum mechanical expression for the polarizability of a molecule in the presence of an electric field that is oscillating at a frequency ω in the z-direction is obtained by using time-dependent perturbation theory (Further information 9.2) and is
The quantities in this expression (which is valid provided that ω is not close to ωn0) are the same as those in the previous Justification, with hωn0 = En (0) − E0 (0). As ω → 0, the equation reduces to eqn 18.10 for the static polarizability. As ω becomes very high (and much higher than any excitation frequency of the molecule so that the ω2 n0 in the denominator can be ignored), the polarizability becomes
That is, when the incident frequency is much higher than any excitation frequency, the polarizability becomes zero. The argument applies to each type of excitation, vibrational as well as electronic, and accounts for the successive decreases in polarizability as the frequency is increased.
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