Square-well interaction between two particles in 3D

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My question is about how one defines (as a function) a square-well type of interaction potential between two particles in 3D space. More precisely, as an analogy, one may have other forms of pair-wise interactions, such as $V(\mathbf r) = e^{-r/r_0}$ where $r$ is the distance between the two particles (point particles assumed), and here the potential $V$ is a quite simple exponential decay.

In contrast, how is the square well case generally defined? I've had two ideas but I don't know if either one is correct: (with $r$ the distance between the points and $a,\epsilon$ two given positive constants.)

  • a) $$ \begin{cases} a & 0 < r < \epsilon \\ 0 & otherwise \end{cases} $$

  • or b) $$ \begin{cases} a & 0 < r_{x,y,z} < \epsilon \\ 0 & otherwise \end{cases} $$

Do either of these definitions correctly represent a square-well type of interaction?

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Conventionally, in the field of interaction potentials, the square well potential is taken to be spherically symmetric (the "square" refers to the shape of the potential curve vs $r$, not to the geometry in 3D). So your answer (a) is closest to the usual one, but not exactly right. Firstly, $a$ should be a negative constant, not a positive one, otherwise it would be a "hump" not a "well". Secondly, it is almost always understood that the square well has been added to an infinitely repulsive hard sphere potential which prevents atoms from overlapping each other. So, most people would understand a square well potential to be (adopting your notation) $$ V(r) = \begin{cases} \infty & r < \sigma \\ -a & \sigma \leq r < \epsilon \\ 0 & r \geq \epsilon \end{cases} $$ with three parameters: $\sigma$ and $\epsilon$, the hard core diameter and well diameter respectively, both positive and with $\sigma<\epsilon$; and $a>0$ (but with an explicit $-$ sign in the formula above), the well depth.

You can find out more about this model, and references to the literature, on the SklogWiki.