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In Moore's introductory physics textbook Six Ideas that Shaped Physics, he describes a set of qualitative rules that first-year physics students can use to sketch energy eigenfunctions in a 1D quantum-mechanical potential. Many of these are basically the WKB formalism in disguise; for example, he introduces a notion of "local wavelength", and justifies the change in amplitude in terms of the classical particle spending more time there. He also notes that the wavefunction must be "wave-like" in the classically allowed region, and "exponential-like" in the classically forbidden region.

However, there is one rule that he uses which seems to work for many (but not all) quantum potentials:

The $n$th excited state $\psi_n(x)$ of a particle in a 1D potential has $n$ extrema.

This is true for the particle in a box (either infinite or finite), the simple harmonic oscillator, the bouncing neutron potential, and presumably a large number of other 1D quantum potentials. It is not true, however, for a particle in a double well of finite depth; the ground state, which has a symmetric wavefunction, has two maxima (one in each potential well) and one minimum (at the midpoint between the wells).

The following questions then arise:

  1. Are there conditions can we place on $V(x)$ that guarantee the above quoted statement is true? For example, is the statement true if $V(x)$ has only one minimum? Is the statement true if the classically allowed region for any energy is a connected portion of $\mathbb{R}$? (The second statement is slightly weaker than the first.)

  2. Can we generalize this statement so that it holds for any potential $V(x)$? Perhaps there is a condition on the number of maxima and minima of $V(x)$ and $\psi_n(x)$ combined?

I suspect that if a statement along these lines can be made, it will come out of the orthogonality of the wavefunctions with respect to some inner product determined by the properties of the potential $V(x)$. But I'm not well-enough versed in operator theory to come up with an easy argument about this. I would also be interested in any interesting counterexamples to this claim that people can come up with.

Qmechanic
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2 Answers2

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I) We consider the 1D time independent Schrödinger equation (TISE) $$ -\psi^{\prime\prime}_n(x) +V(x)\psi_n(x) ~=~ E_n\psi_n(x) \tag{1}$$ on the real line $\mathbb{R}$.

II) From a physics$^{\dagger}$ perspective, the most important conditions are:

  1. That there exists a ground state $\psi_1$.

  2. That we only consider eigenvalues $$ E_n ~<~\liminf_{x\to \pm\infty}~ V(x). \tag{2}$$ Eq. (2) implies the boundary conditions (BCs) $$ \lim _{x\to \pm\infty} \psi_n(x)~=~0 .\tag{3}$$ We can then consider $x=\pm\infty$ as 2 boundary nodes.

Remark: We may argue that the wavefunction $\psi_n$ is differentiable, cf. e.g. my Phys.SE answer here. We will assume that from now on.

Remark: Using complex conjugation on TISE (1), we can without loss of generality assume that $\psi_n$ is real and normalized, cf. e.g. this Phys.SE post. We will assume that from now on.

Lemma 1: The eigenvalues $E_n$ are non-degenerate.

Sketched proof of Lemma 1: The Wronskian of 2 eigenfunctions is a constant. By BCs the constant is zero. Then the 2 eigenfunctions are proportional, cf. e.g. this Phys.SE post. $\Box$

Remark: It follows from a Wronskian argument applied to two eigenfunctions, that the eigenvalues $E_n$ are non-degenerate.

Remark: A double (or higher) node $x_0$ cannot occur, because it must obey $\psi_n(x_0)=0=\psi^{\prime}_n(x_0)$. The uniqueness of a 2nd order ODE then implies that $\psi_n\equiv 0$. Contradiction.

III) Define

$$ \nu(n)~:=~|\{\text{interior nodes of }\psi_n\}|,\tag{4}$$

$$ M_+(n)~:=~|\{\text{local max points $x_0$ for $|\psi_n|$ with }\psi_n(x_0)>0\}|,\tag{5}$$

$$ M_-(n)~:=~|\{\text{local max points $x_0$ for $|\psi_n|$ with }\psi_n(x_0)<0\}|,\tag{6}$$

$$ m_+(n)~:=~|\{\text{local min points $x_0$ for $|\psi_n|$ with }\psi_n(x_0)>0\}|,\tag{7}$$

$$ m_-(n)~:=~|\{\text{local min points $x_0$ for $|\psi_n|$ with }\psi_n(x_0)<0\}|,\tag{8}$$

$$ M(n)~:=~|\{\text{local max points for }|\psi_n|\}|~=~M_+(n)+M_-(n), \tag{9}$$

$$ m(n)~:=~|\{\text{local min points $x_0$ for $|\psi_n|$ with }\psi_n(x_0)\neq 0\}|~=~m_+(n)+m_-(n), \tag{10}$$

$$\Delta M_{\pm}(n)~:=~M_{\pm}(n)-m_{\pm}(n)~\geq~0.\tag{11} $$

Observation. Local max (min) points for $|\psi_n|\neq 0$ can only occur in classical allowed (forbidden) intervals, i.e. oscillatory (exponential) intervals, respectively.

Note that the roles of $\pm$ flip if we change the overall sign of the real wave function $\psi_n$.

Proposition. $$ \begin{align}\Delta M_+(n)+\Delta M_-(n)~=~&\nu(n)+1, \cr |\Delta M_+(n)-\Delta M_-(n)|~=~&2~{\rm frac}\left(\frac{\nu(n)+1}{2}\right).\end{align}\tag{12} $$

Sketched proof: Use Morse-like considerations. $\Box$

IV) Finally let us focus on the nodes.

Lemma 2. If $E_n<E_m$, then for every pair of 2 consecutive (possibly boundary) nodes $a$ and $b$ for the eigenfunction $\psi_n$, the eigenfunction $\psi_m$ has at least one node $c$ strictly in-between.

Sketched proof of Lemma 2: Assume that the eigenfunction $\psi_n>0$ is positive in the open interval $]a,b[$. (The negative case is similar, and left to the reader.) Use a Wronskian argument applied to $\psi_n$ and $\psi_m$, cf. Refs. 1-2: $$\begin{align} \underbrace{\psi^{\prime}_n(a)}_{>0}\psi_m(a)-\underbrace{\psi^{\prime}_n(b)}_{<0}\psi_m(b) ~=~&\left[-\psi^{\prime}_n(x)\psi_m(x)\right]_{x=a}^{x=b}\cr ~=~&\left[W(\psi_n,\psi_m)\right]_{x=a}^{x=b}\cr ~=~&\int_a^b\!dx\frac{d}{dx}W(\psi_n,\psi_m)\cr ~\stackrel{(1)}{=}~&\underbrace{(E_n-E_m)}_{<0}\int_a^b\!dx\underbrace{\psi_n(x)}_{> 0\text{ in bulk}}\psi_m(x).\end{align}\tag{13}$$ Eq. (13) cannot hold if $\psi_m$ does not change sign in the open interval $]a,b[$. $\Box$

Node theorem. With the above assumptions from Section II, the $n$'th eigenfunction $\psi_n$ has $$\nu(n)~=~n\!-\!1.\tag{14}$$

Sketched proof of the node theorem:

  1. $\nu(n) \geq n\!-\!1$: Use Lemma 2. $\Box$

  2. $\nu(n) \leq n\!-\!1$: Truncate eigenfunction $\psi_n$ such that it is only supported between 2 consecutive nodes. If there are too many nodes there will be too many independent eigenfunctions in a min-max variational argument, leading to a contradiction, cf. Ref. 1. $\Box$

Remark: Refs. 2-3 feature an intuitive heuristic argument for the node theorem: Imagine that $V(x)=V_{t=1}(x)$ belongs to a continuous 1-parameter family of potential $V_{t}(x)$, $t\in[0,1]$, such that $V_{t=0}(x)$ satisfies property (4). Take e.g. $V_{t=0}(x)$ to be the harmonic oscillator potential or the infinite well potential. Now, if an extra node develops at some $(t_0,x_0)$, it must be a double/higher node. Contradiction.

References:

  1. R. Hilbert & D. Courant, Methods of Math. Phys, Vol. 1; Section VI.

  2. M. Moriconi, Am. J. Phys. 75 (2007) 284, arXiv:quant-ph/0702260.

  3. B. Zwiebach, Node Theorem, MIT OCW (2016).


$^{\dagger}$ For a more rigorous mathematical treatment, consider asking on MO.SE or Math.SE.

Qmechanic
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Here is the outline of a proof. This outline relies on Knesser's theorem and the Sturm-Picone comparison theorem.

We begin with an application of Knesser's theorem [1]. We have an ordinary linear homogeneous differential equation of the form $$\psi'' + \frac{2m}{\hbar^2}(E-U(x))\psi = 0$$ with constants $m$, $\hbar$, and $E$ and with $U: [0,+\infty) \to \mathbb{R}$ is a continuous function. Please note that a more rigorous proof might include a distinct domain from that provided here. Knesser explains that this equation is oscillating if it has a solution $\psi$ with infinitely many zeros, and non-oscillating otherwise.

The theorem state if $$:\liminf_{x \to +\infty} x^2 \frac{2m}{\hbar^2}(E-U(x)) > \frac{1}{4},$$ then that the equation is oscillating.

Going forward let's go ahead and suppose that $$:\liminf_{x \to +\infty} x^2 \frac{2m}{\hbar^2}(E-U(x)) > \frac{1}{4}.$$

Next we apply the Sturm-Picone comparison theorem [2]. Let $U(x)$ be a real on the interval $[a,b]$ and let \begin{align} \psi'' + \frac{2m}{\hbar^2}(E_k-U(x))\psi = 0 \tag{10} \\ \psi'' + \frac{2m}{\hbar^2}(E_{k+1}-U(x))\psi = 0 \tag{20} \end{align} be two homogeneous linear second order differential equations in self-adjoint form with $E_{k+1}> E_{k}$. Let $u$ be a non-trivial solution of (10) with successive roots at $z_1$ and $z_2$ and let $v$ be a non-trivial solution of (20). Then, since the eigenfunctions are orthonormal for distinct eigenvalues (i.e., distinct values of $E$) the following properties holds. There exists an $x$ in $(z_1, z_2)$ such that $v(x) = 0$.

Allow, for example, that the eigenvector associated with the first eigenvalue $E_1$ has two roots: one at $a$ and the other at $b$. It is an oscillatory solution so there is one global extrema between $a$ and $b$. The Sturm-Picone comparison theorem tells us that the first-excited states eigenvector will have another root between $a$ and $b$. Thus, it will have two global extrema between $a$ and $b$. So on and so forth.

Bibliography

[1] https://en.wikipedia.org/wiki/Kneser%27s_theorem_(differential_equations)

[2] https://en.wikipedia.org/wiki/Sturm%E2%80%93Picone_comparison_theorem

Michael Levy
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