Quantum Mechanics – Are All Atoms Spherically Symmetric and Why Are Half-Filled Sub-Shells Especially Symmetric

angular momentumatomic-physicsatomsorbitalsquantum mechanics

In my atomic physics notes they say

In general, filled sub-shells are spherically symmetric and set up, to a good approximation, a central field.

However sources such as here say that, even for the case of a single electron in Hydrogen excited to the 2p sub-shell, the electron is really in a spherically symmetric superposition $\frac{1}{\sqrt3}[2p_x+2p_y+2p_z]$ (which I thought made sense since there should be no preferred direction in space).

My question there now is, why is the central field approximation only an approximation if all atoms are really perfectly spherically symmetric, and why are filled/half-filled sub-shells 'especially spherically symmetric?

Best Answer

In general, atoms need not be spherically symmetric.

  • The source you've given is flat-out wrong. The wavefunction it mentions, $\varphi=\frac{1}{\sqrt3}[2p_x+2p_y+2p_z]$, is in no way spherically symmetric. This is easy to check: the wavefunction for the $2p_z$ orbital is $\psi_{2p_z}(\mathbf r)=\frac {1}{\sqrt {32\pi a_0^5}}\:z \:e^{-r/2a_{0}}$ (and similarly for $2p_x$ and $2p_y$), so the wavefunction of the combination is $$\varphi(\mathbf r)=\frac {1}{\sqrt {32\pi a_0^5}}\:\frac{x+y+z}{\sqrt 3} \:e^{-r/2a_{0}},$$ i.e., a $2p$ orbital oriented along the $(\hat{x}+\hat y+\hat z)/\sqrt3$ axis.

    This is an elementary fact and it can be verified at the level of an undergraduate text in quantum mechanics (and it was also obviously wrong in the 1960s). It is extremely alarming to see it published in an otherwise-reputable journal.

  • On the other hand, there are some states of the hydrogen atom in the $2p$ shell which are spherically symmetric, if you allow for mixed states, i.e., a classical probabilistic mixture $\rho$ of hydrogen atoms prepared in the $2p_x$, $2p_y$ and $2p_z$ states with equal probabilities. It is important to emphasize that it is essential that the mixture be incoherent (i.e. classical and probabilistic, as opposed to a quantum superposition) for the state to be spherically symmetric.

  • As a general rule, if all you know is that you have "hydrogen in the $2p$ shell", then you do not have sufficient information to know whether it is in a spherically-symmetric or an anisotropic state. If that's all the information available, the initial presumption is to take a mixed state, but the next step is to look at how the state was prepared:

    • The $2p$ shell can be prepared through isotropic processes, such as by excitation through collisions with a non-directional beam of electrons of the correct kinetic energy. In this case, the atom will be in a spherically-symmetric mixed state.
    • On the other hand, it can also be prepared via anisotropic processes, such as photo-excitation with polarized light. In that case, the atom will be in an anisotropic state, and the direction of this anisotropy will be dictated by the process that produced it.

    It is extremely tempting to think (as discussed previously e.g. here, here and here, and links therein) that the spherical symmetry of the dynamics (of the nucleus-electron interactions) must imply spherical symmetry of the solutions, but this is obviously wrong $-$ to start with, it would apply equally well to the classical problem! The spherical symmetry implies that, for any anisotropic solution, there exist other, equivalent solutions with complementary anisotropies, but that's it.

  • The hydrogen case is a bit special because the $2p$ shell is an excited state, and the ground state is symmetric. So, in that regard, it is valid to ask: what about the ground states of, say, atomic boron? If all you know is that you have atomic boron in gas phase in its ground state, then indeed you expect a spherically-symmetric mixed state, but this can still be polarized to align all the atoms into the same orientation.

    As a short quip: atoms can have nontrivial shapes, but the fact that we don't know which way those shapes are oriented does not make them spherically symmetric.

  • So, given an atom (perhaps in a fixed excited state), what determines its shape? In short: its term symbol, which tells us its angular momentum characteristics, or, in other words, how it interacts with rotations.

    • The only states with spherical symmetry are those with vanishing total angular momentum, $J=0$. If this is not the case, then there will be two or more states that are physically distinct and which can be related to each other by a rotation.
    • It's important to note that this anisotropy could be in the spin state, such as with the $1s$ ground state of hydrogen. If you want to distinguish the states with isotropic vs anisotropic charge distributions, then you need to look at the total orbital angular momentum, $L$. The charge distribution will be spherically symmetric if and only if $L=0$.

    A good comprehensive source for term symbols of excited states is the Levels section of the NIST ASD.

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