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12.4: Dirac Theory of the Hydrogen Atom

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    The theory of Paul Dirac represents an attempt to unify the theories of quantum mechanics and special relativity. That is, one seeks a formulation of quantum mechanics which is Lorentz invariant, and hence consistent with special relativity. For a free particle, relativity states that the energy is given by

    \[E + p^2c^2 + m^2c^4\]

    Associating \(E\) with a Hamiltonian in quantum mechanics, one has

    \[H^2 = p^2c^2 + m^2c^4 \label{59}\]

    If \(H\) and \(p\) are associated with the same operators as in Schrödinger theory, then one expects the wave equation

    \[ - \hbar \dfrac{\partial^2}{\partial t^2} \Psi = ( -\hbar^2 \nabla^2 c^2 + m^2 c^4) \Psi \label{60}\]

    This is known as the Klein-Gordan Equation. Unfortunately, attempts to utilize this equation are not successful, since that which one would wish to interpret as a probability distribution turns out to be not positive definite. To alleviate this problem, the square root may be taken to get

    \[ H = \sqrt{ p^2c^2 + m^2c^4} \label{61}\]

    However, this creates a new problem. What is meant by the square root of an operator? The approach is to guess the form of the answer, and the correct guess turns out to be

    \[H = c \alpha \cdot p + \beta mc^2 \label{62}\]

    With this form of the Hamiltonian, the wave equation can be written

    \[ i \hbar \dfrac{\partial \chi}{\partial t} = (c \alpha \cdot p + \beta mc^2) \chi \label{63}\]

    In order for this to be valid, one hopes that when it is squared the Klein-Gordan equation is recovered. For this to be true, Equation \(\ref{63}\) must be interpreted as a matrix equation, where \(\alpha\) and \(\beta\) are at least \(4 \times 4\) matrices and the wavefunction tex2html_wrap_inline1624 is a four-component column matrix.

    It turns out that Equation \(\ref{63}\) describes only a particle with spin 1/2. This is fine for application to the hydrogen atom, since the electron has spin 1/2, but why should it be so? The answer is that the linearization of the Klein-Gordan equation is not unique. The particular linearization used here is the simplest one, and happens to describe a particle of spin 1/2, but other more complicated Hamiltonians may be constructed to describe particles of spin 0,1,5/2 and so on. The fact that the relativistic Dirac theory automatically includes the effects of spin leads to an interesting conclusion - spin is a relativistic effect. It can be added by hand to the non-relativistic Schödinger theory with satisfactory results, but spin is a natural consequence of treating quantum mechanics in a completely relativistic fashion.

    Spin is a relativistic effect

    Including the potential now in the Hamiltonian, Equation \(\ref{63}\) becomes


    When the square root was taken to linearize the Klein-Gordan equation, both a positive and a negative energy solution was introduced. One can write the wavefunction


    where \(\Psi_+\) represents the two components of \(\chi\) associated with the positive energy solution and \(\Psi_-\) represents the components associated with the negative energy solution. The physical interpretation is that \(\Psi_+\) is the particle solution, and \(\Psi_-\) represents an anti-particle. Anti-particles are thus predicted by Dirac theory, and the discovery of anti-particles obviously represents a huge triumph for the theory. In hydrogen, however, the contribution of \(\Psi_-\) is small compared to \(\Psi_+\). With enough effort, the equations for \(\Psi_+\) and \(\Psi_-\) can be decoupled to whatever order is desired. When this is done, the Hamiltonian to order \(v^2/c^2\) can be written

    \[ H + H_s + \Delta H _{rel} + \Delta H_{so} + \Delta H_d \label{66}\]


    • \(H_s\) is the original Schrödinger Hamiltonian,
    • \(\Delta H _{rel}\) is the relativistic correction to the kinetic energy,
    • \(\Delta H_{so}\) is the spin-orbit term, and
    • \(\Delta H_d\) is the previously mentioned Darwin term.

    The Darwin Term

    The physical origin of the Darwin term is a phenomenon in Dirac theory called zitterbewegung, whereby the electron does not move smoothly, but instead undergoes extremely rapid small-scale fluctuations, causing the electron to see a smeared-out Coulomb potential of the nucleus.

    The Darwin term may be written

    \[ \Delta H_d = -\dfrac{e\hbar^2}{8m^2c^2} \nabla^2 \Psi \label{67}\]

    For the hydrogenic-atom potential \( V = \dfrac{Ze}{r}\), Equation \(\ref{67}\) is

    \[ H_d = -\dfrac{Ze^2\pi \hbar^2}{2 m^2c^2} \delta^3(r) \label{68}\]

    When first-order perturbation theory is applied, the energy correction depends on \(| \Psi(0)|^2\). This term will only contribute for s states (i.e., (l=0)), since only these wavefunctions have non-zero probability for finding the electron at the origin. The energy correction for \(l=0\) can be calculated to be

    \[ \Delta E _d = (Z \alpha)^4 mc^2 \dfrac{1}{2n^3} \label{69}\]

    Including this term, the fine-structure splitting given by Equation \(\ref{58}\) can be reproduced for all \(l\). All the effects that go into fine structure are thus a natural consequence of the Dirac theory.

    Contributors and Attributions

    • Randal Telfer (JWST Astronomical Optics Scientist, Space Telescope Science Institute)

    This page titled 12.4: Dirac Theory of the Hydrogen Atom is shared under a CC BY-NC-SA 2.0 license and was authored, remixed, and/or curated by Niels Walet via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.

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