Magnetic dipole–dipole interaction

Magnetic dipole–dipole interaction, also called dipolar coupling, refers to the direct interaction between two magnetic dipoles. Roughly speaking, the magnetic field of a dipole goes as the inverse cube of the distance, and the force of its magnetic field on another dipole goes as the first derivative of the magnetic field. It follows that the dipole-dipole interaction goes as the inverse fourth power of the distance.

Suppose m₁ and m₂ are two magnetic dipole moments that are far enough apart that they can be treated as point dipoles in calculating their interaction energy. The potential energy H of the interaction is then given by:

<math> H = -\frac{\mu_0}{4\pi|\mathbf r|^3}\left[ 3(\mathbf m_1\cdot\hat\mathbf r)(\mathbf m_2\cdot\hat\mathbf r) - \mathbf m_1\cdot\mathbf m_2\right]-\mu_0 \frac{2}{3} \mathbf m_1\cdot\mathbf m_2 \delta(\mathbf r), </math>

where μ₀ is the magnetic constant, r̂ is a unit vector parallel to the line joining the centers of the two dipoles, and |r| is the distance between the centers of m₁ and m₂. Last term with <math>\delta</math>-function vanishes everywhere but the origin, and is necessary to ensure that <math>\nabla\cdot\mathbf B</math> vanishes everywhere. Alternatively, suppose γ₁ and γ₂ are gyromagnetic ratios of two particles with spin quanta S₁ and S₂. (Each such quantum is some integral multiple of 1/2.) Then:

<math> H = -\frac{\mu_0\gamma_1\gamma_2\hbar^2}{4\pi|\mathbf r|^3 } \left[3(\mathbf S_1 \cdot\hat\mathbf r)(\mathbf S_2\cdot\hat\mathbf r)-\mathbf S_1\cdot\mathbf S_2\right] ,</math>

where <math>\hat\mathbf r</math> is a unit vector in the direction of the line joining the two spins, and |r| is the distance between them.

Finally, the interaction energy can be expressed as the dot product of the moment of either dipole into the field from the other dipole:

<math> H = -\mathbf m_1\cdot{\mathbf B}_2({\mathbf r}_1)=-\mathbf m_2\cdot{\mathbf B}_1({\mathbf r}_2), </math>

where B₂(r₁) is the field that dipole 2 produces at dipole 1, and B₁(r₂) is the field that dipole 1 produces at dipole 2. It is not the sum of these terms.

The force F arising from the interaction between m₁ and m₂ is given by:

<math>

\mathbf F = \frac{3\mu_0}{4\pi|\mathbf r|^4}\{(\hat\mathbf r\times\mathbf m_1)\times\mathbf m_2 +(\hat\mathbf r\times\mathbf m_2)\times\mathbf m_1 - 2 \hat\mathbf r(\mathbf m_1 \cdot \mathbf m_2) + 5\hat\mathbf r[(\hat\mathbf r\times\mathbf m_1)\cdot(\hat\mathbf r\times \mathbf m_2)]\}.</math>

The Fourier transform of H can be calculated from the fact that

<math> \frac{3 (\mathbf m_1\cdot\hat\mathbf r)(\mathbf m_2\cdot\hat\mathbf r) - \mathbf m_1\cdot\mathbf m_2}{4\pi|\mathbf r|^3} = (\mathbf m_1\cdot\mathbf \nabla)(\mathbf m_2\cdot\mathbf \nabla)\frac{1}{4\pi |\mathbf r|} </math>

and is given by

<math> H = {\mu_0}\frac{ (\mathbf m_1\cdot\mathbf q)(\mathbf m_2\cdot\mathbf q) - |\mathbf q|^2 \mathbf m_1\cdot\mathbf m_2}{|\mathbf q|^2}. </math>

Dipolar coupling and NMR spectroscopy

The direct dipole-dipole coupling is very useful for molecular structural studies, since it depends only on known physical constants and the inverse cube of internuclear distance. Estimation of this coupling provides a direct spectroscopic route to the distance between nuclei and hence the geometrical form of the molecule, or additionally also on intermolecular distances in the solid state leading to NMR crystallography notably in amorphous materials.

For example, in water, NMR spectra of hydrogen atoms of water molecules are narrow lines because dipole coupling is averaged due to chaotic molecular motion.<ref>Abragam, A. (1961) The Principles of Nuclear Magnetism. Oxford University Press, Oxford.</ref> In solids, where water molecules are fixed in their positions and do not participate in the diffusion mobility, the corresponding NMR spectra have the form of the Pake doublet. In solids with vacant positions, dipole coupling is averaged partially due to water diffusion which proceeds according to the symmetry of the solids and the probability distribution of molecules between the vacancies.<ref>Gabuda, S.P.; Lundin, A.G.(1969) Diffusion of Water Molecules in Hydrates and NMR Spectra. JETP, 28 (3), 555. http://www.jetp.ac.ru/cgi-bin/dn/e_028_03_0555.pdf</ref>

Although internuclear magnetic dipole couplings contain a great deal of structural information, in isotropic solution, they average to zero as a result of diffusion. However, their effect on nuclear spin relaxation results in measurable nuclear Overhauser effects (NOEs).

The residual dipolar coupling (RDC) occurs if the molecules in solution exhibit a partial alignment leading to an incomplete averaging of spatially anisotropic magnetic interactions i.e. dipolar couplings. RDC measurement provides information on the global folding of the protein-long distance structural information. It also provides information about "slow" dynamics in molecules.

See also

• J-coupling
• Magic angle
• Residual dipolar coupling
• Nuclear Overhauser effect
• Magnetic moment
• Zero field splitting

References

• Malcolm H. Levitt, Spin Dynamics: Basics of Nuclear Magnetic Resonance. ISBN 0-471-48922-0.