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The interaction of an electromagnetic wave with an electron bound in an atom or molecule can be described by time-dependent
perturbation theory In mathematics and applied mathematics, perturbation theory comprises methods for finding an approximate solution to a problem, by starting from the exact solution of a related, simpler problem. A critical feature of the technique is a middle ...
. Magnetic dipole transitions describe the dominant effect of the coupling of the magnetic dipole moment of the electron to the magnetic part of the electromagnetic wave. They can be divided into two groups by the frequency at which they are observed: optical magnetic dipole transitions can occur at frequencies in the infrared, optical or ultraviolet between sublevels of two different electronic levels, while magnetic resonance transitions can occur at microwave or radio frequencies between angular momentum sublevels within a single electronic level. The latter are called
Electron Paramagnetic Resonance Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spin ...
(EPR) transitions if they are associated with the electronic angular momentum of the atom or molecule and
Nuclear Magnetic Resonance Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are disturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a ...
(NMR) transitions if they are associated with the nuclear angular momentum.


Theoretical description

The Hamiltonian of a bare electron bound in an atom interacting with a time-dependent electromagnetic field is given by the
Pauli equation In quantum mechanics, the Pauli equation or Schrödinger–Pauli equation is the formulation of the Schrödinger equation for spin-1/2 particles, which takes into account the interaction of the particle's spin with an external electromagnetic f ...
(the theoretical description follows ): H=\frac mathbf-q\mathbf(\mathbf,t)2+V(R)-\frac\mathbf \cdot \mathbf(\mathbf,t) where q and m are the charge and mass of a bare electron, \mathbf is the spin operator, \mathbf(\mathbf,t) is the vector potential of the wave and \mathbf is the momentum operator. The Hamiltonian can be split into a time independent and a time dependent part: H=H_0+W(t) with H_0=\frac \mathbf^2 +V(R) the atomic Hamiltonian and the interaction with the electromagnetic wave (time-dependent): W(t)=-\frac \mathbf\cdot \mathbf(\mathbf,t)-\frac \mathbf\cdot \mathbf(\mathbf,t)+\frac \mathbf^2(\mathbf,t) Since the last term is quadratic in A it can be neglected for small fields. The time-dependent part can be Taylor expanded in terms belonging to electric transition dipole (from the first term), magnetic transition dipole (from the second term), and higher order terms, such as electric quadropole and so on. The term belonging to the magnetic transition dipole is: W_(t)=-\frac (\mathbf+2\mathbf)\cdot\mathbf(\mathbf,t)


Selection rules

The
selection rule In physics and chemistry, a selection rule, or transition rule, formally constrains the possible transitions of a system from one quantum state to another. Selection rules have been derived for electromagnetic transitions in molecules, in atoms, in ...
s for allowed magnetic dipole transitions are: 1. \Delta J=0,\pm 1 (\text J=0 \rightarrow J=0) (J:
total angular momentum quantum number In quantum mechanics, the total angular momentum quantum number parametrises the total angular momentum of a given particle, by combining its orbital angular momentum and its intrinsic angular momentum (i.e., its spin). If s is the particle's sp ...
) 2. \Delta M_J=0,\pm 1 (M_J: projection of the
total angular momentum In quantum mechanics, the total angular momentum quantum number parametrises the total angular momentum of a given particle, by combining its orbital angular momentum and its intrinsic angular momentum (i.e., its spin). If s is the particle's ...
along a specified axis) 3. No parity change


Comparison to electric dipole transitions

*
Electric dipole transition An electric dipole transition is the dominant effect of an interaction of an electron in an atom with the electromagnetic field. Following reference, consider an electron in an atom with quantum Hamiltonian H_0 , interacting with a plane electr ...
s only have a non-vanishing matrix element between quantum states with different parity. *Magnetic dipole transitions and electric quadrupole transitions in contrast couple states with the same parity. The response of these two transitions is much weaker than that of electric dipole transitions. *The electronic states of atoms and molecules normally don't have a static electric dipole moment but many states have a static magnetic dipole moment. The classical magnetized top model can be used to describe magnetic resonances for atoms with static magnetic dipole moment between different Zeeman-split-sublevel in a sufficient way without needing a full quantum mechanical description.


References

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External links


National Institute of Standards and Technology
Magnetism