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Though essentially present in all substances, diamagnetism is a much weaker effect and therefore, often suppressed by relatively strong opposite effects, like paramagnetism. This effect is exclusively observed in those solids which do not carry any permanent, intrinsic magnetic (dipole) moment i.e., does not contain unpaired valence electrons. The existence of a very small non-zero magnetic moments for these materials is attributed to the orbital motion of electrons.

Why is then that in absence of an external magnetic field, the macroscopic magnetization is zero? How do we understand this from classical Langevin theory and quantum theory?

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I don't think your question needs quantum physics to explain it.

First of all, all materials do have diamagnetic contributions, and generically that is independent of whether intrinsic magnetic moments exist or not; all you need is charge. Even Quantum treatments (as done by Langevin or Landau for example) do not require pre-existing magnetic moments.

Consider the case of a free electron plasma in thermal equilibrium. By the Bohr-van Leeuwen theorem, there cannot be a net magnetic moment for the plasma in equilibrium. Now turn on a magnetic field. The system will leave equilibrium and will generate a current opposing the magnetic field (I.e. Faraday's law). This finite current implies a net magnetic moment, meaning the plasma is diamagnetic.

If one were to ask in this situation, "Why is then that in absence of an external magnetic field, the macroscopic magnetization is zero?" The answer is that there was no reason for moments to line up (no exchange interaction, etc.)

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  • $\begingroup$ I can add more information and correct mistakes in the answer, would OP (or whoever) mind explaining the downvote? I believe the question itself presumes the existence of magnetic moments, and that is incorrect in general. $\endgroup$ – KF Gauss Apr 21 '17 at 22:58

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