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How to quantize a system if kinetic energy depends on coordinate?

Physics Asked on July 25, 2021

In a standard physics course we usually learn that quantization of a system is ambiguous if momentum and position happen to be multiplied in the classical Hamiltonian (i.e. the classical Hamiltonian contains a term like $xp$). This ambiguity of quantization seemed more like of an academic interest to me, until I tried to quantize this simple classical system.

Suppose we want to model the oscillations of an electron bubble in a system of solvated electrons. If an alkali metal atom, for instance sodium, is thrown into liquid ammonia (NH$^3$), the ammonia dissolves the metal atom it into Na$^+$ ion and $e^-$ ion (see a video of dissolution here). The $e^-$ ion is formed by ammonia turning with more positively charged hydrogen towards electron, forming a cavity of the radius $Rapprox 0.32$ nm around the electron. The electron occupies the lowest energy level inside the cavity. I would like to model radial quantum oscillation of the bubble within adiabatic approximation, where the energy of the electron is added to the effective potential energy of the bubble (the static bubble model was developed by Cohen and Thompson in 1968; for a free access review paper see here).

From a classical picture, everything is more or less clear. The potential energy of the bubble is assumed to consist of the polarization energy, electron energy and energy of surface tension, and it is a function of the radius of the bubble. The kinetic energy of the bubble is assumed to consist only of the kinetic energy of the liquid around the bubble. The liquid is assumed to be continuous and incompressible, and the bubble is assumed perfectly spherical. Classical Lagrangian looks like this:
$$
L(R,dot{R})=K-Pi=4pi rho Rfrac{dot{R}^2}{2}-Pi(R).tag{1}
$$

The corresponding classical Hamiltonian looks like this:
$$
H=frac{1}{4pirho R}frac{p^2}{2}+Pi(R).tag{2}
$$

Now, I know I cannot quantize the system naively by substituting $prightarrow hat{p}$ and $Rrightarrow hat{R}$ into the Hamiltonian, because the kinetic energy contains the product $R$ and $p$, which do not commute. Is there any good way of quantizing such system? What do people usually do, if they find that kinetic energy of the classical Hamiltonian depends on the position?

One Answer

The simplest idea is to reorder the Hamiltonian operator in a Hermitian fashion, e.g., $$ hat{H}~=~hat{p}frac{1}{8pirho hat{R}}hat{p}+Pi(hat{R}).$$ See also e.g. this related Phys.SE post.

Answered by Qmechanic on July 25, 2021

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