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Free Physics Study Material for CSIR NET, IIT JAM, GATE, JEST & TIFR

by Pravegaa Education
Chapter 11

Radial Wave Function and Hydrogen Atom

11.1  Central Force Problem

  • Central potential: \(V=V(r)\) \(\Rightarrow\vec F=-\dfrac{\partial V}{\partial r}\hat r\), zero torque, angular momentum conserved \(\Rightarrow[\hat H,\hat L^2]=[\hat H,\hat L_z]=0\).

  • Hence eigenfunctions of \(\hat H\) can be chosen as eigenfunctions of \(\hat L^2\), \(\hat L_z\): \[\psi(r,\theta,\phi)=R(r)\,Y_l^m(\theta,\phi).\]

Radial normalization and probability density

  • \(\displaystyle\iiint|\psi|^2r^2\sin\theta\,dr\,d\theta\,d\phi=\int_0^\infty|R|^2r^2dr\cdot\underbrace{\iint|Y_l^m|^2\sin\theta\,d\theta\,d\phi}_{=1}=1\).

  • Radial normalization: \(\displaystyle\int_0^\infty|R(r)|^2r^2dr=1\).

  • Radial probability density: \(\rho(r)=|R(r)|^2r^2\) — area under it is 1.

Radial equation

  • \(-\dfrac{\hbar^2}{2m}\nabla^2\psi+V\psi=E\psi\) with \(\nabla^2=\dfrac{1}{r^2}\dfrac{\partial}{\partial r}\Big(r^2\dfrac{\partial}{\partial r}\Big)-\dfrac{\hat L^2}{\hbar^2r^2}\) and \(\hat L^2Y_l^m=l(l+1)\hbar^2Y_l^m\): \[-\frac{\hbar^2}{2m}\Big[\frac{d^2R}{dr^2}+\frac2r\frac{dR}{dr}\Big]+\Big[\frac{l(l+1)\hbar^2}{2mr^2}+V(r)\Big]R=ER.\]

  • First term: radial (translational) kinetic energy; \(\dfrac{l(l+1)\hbar^2}{2mr^2}\): rotational/centrifugal term; bracket: effective potential.

  • Substitute \(R=u(r)/r\) (\(\frac{d}{dr}(r^2R')=ru''\)): \[-\frac{\hbar^2}{2m}\frac{d^2u}{dr^2}+\Big[V(r)+\frac{l(l+1)\hbar^2}{2mr^2}\Big]u=Eu,\qquad \int_0^\infty|u|^2dr=1.\]

11.2  Particle in an Infinite Spherical Well

  • \(V(r)=0\) for \(r<a\); \(\infty\) for \(r>a\). Take \(l=0\).

  • \(r>a\): \(u=0\).   \(r<a\): \(u''+k^2u=0\), \(k=\sqrt{2mE}/\hbar\) \(\Rightarrow u=A\sin kr+B\cos kr\).

  • \(R=u/r\) finite at \(r=0\) \(\Rightarrow B=0\);   \(R(a)=0\Rightarrow ka=n\pi\): \[E_{n00}=\frac{n^2\pi^2\hbar^2}{2ma^2},\qquad R_{n0}(r)=\sqrt{\frac2a}\,\frac{\sin(n\pi r/a)}{r}\;(r<a),\qquad n=1,2,3,\ldots\]

  • Normalization: \(|A|^2\int_0^a\sin^2\frac{n\pi r}{a}dr=1\Rightarrow A=\sqrt{2/a}\).

  • \(\psi_{n00}=R_{n0}Y_0^0=\dfrac{1}{\sqrt{2\pi a}}\,\dfrac1r\sin\dfrac{n\pi r}{a}\) for \(r<a\), zero otherwise.

Example 11.1   Ground state of the spherical well

For \(l=0\): (a) write the ground state and its energy; (b) plot \(R(r)\); (c) plot \(\rho(r)\).

Solution

  • (a)  \(\psi_{100}=\dfrac{1}{\sqrt{2\pi a}}\,\dfrac{\sin(\pi r/a)}{r}\),   \(E_{100}=\dfrac{\pi^2\hbar^2}{2ma^2}\).

  • (b)  \(R(r)=\sqrt{\frac2a}\dfrac{\sin(\pi r/a)}{r}\): finite (\(=\sqrt{2/a}\,\pi/a\)) at \(r=0\), falling to zero at \(r=a\).

  • (c)  \(\rho(r)=\dfrac2a\sin^2\dfrac{\pi r}{a}\): zero at both ends, peak at \(r=a/2\).

Figure   Figure

Example 11.2   Expectation values in the spherical well

For \((n,0,0)\): (a) \(P(0<r<a/2)\); (b) \(\left\langle r\right\rangle\); (c) \(\left\langle x\right\rangle,\left\langle y\right\rangle,\left\langle z\right\rangle\).

Solution

  • (a)  \(P=\dfrac2a\displaystyle\int_0^{a/2}\sin^2\frac{n\pi r}{a}dr=\frac12\) (for every \(n\)).

  • (b)  \(\left\langle r\right\rangle=\dfrac2a\displaystyle\int_0^ar\sin^2\frac{n\pi r}{a}dr=\frac a2\).

  • (c)  \(\left\langle x\right\rangle\propto\int_0^{2\pi}\cos\phi\,d\phi=0\); likewise \(\left\langle y\right\rangle=\left\langle z\right\rangle=0\) (spherical symmetry).

11.3  The Hydrogen Atom

  • Proton (fixed at the origin) plus electron bound by \(V(r)=-\dfrac{e^2}{4\pi\epsilon_0r}\) — a central potential, so \(\psi=R(r)Y_l^m\).

  • With \(R=u/r\) and \(k=\sqrt{-2mE}/\hbar\) (\(E<0\)), \(\rho=kr\), \(\rho_0=\dfrac{me^2}{2\pi\epsilon_0\hbar^2k}\): \[\frac{d^2u}{d\rho^2}=\Big[1-\frac{\rho_0}{\rho}+\frac{l(l+1)}{\rho^2}\Big]u.\]

Asymptotic behaviour

  • \(\rho\to\infty\): \(u''=u\Rightarrow u\sim e^{-\rho}\) (the \(e^{\rho}\) solution diverges).

  • \(\rho\to0\): \(u''=\frac{l(l+1)}{\rho^2}u\Rightarrow u\sim\rho^{l+1}\) (the \(\rho^{-l}\) solution diverges).

  • Try \(u(\rho)=\rho^{l+1}e^{-\rho}v(\rho)\): \[\rho v''+2(l+1-\rho)v'+\big[\rho_0-2(l+1)\big]v=0.\]

Series solution and quantization

  • \(v=\sum_jc_j\rho^j\) gives \[c_{j+1}=\frac{2(j+l+1)-\rho_0}{(j+1)(j+2l+2)}\,c_j.\]

  • For large \(j\), \(c_{j+1}\approx\frac{2}{j+1}c_j\Rightarrow v\sim e^{2\rho}\Rightarrow u\sim\rho^{l+1}e^{\rho}\) — diverges. The series must terminate at \(j_{\max}\): \[2(j_{\max}+l+1)=\rho_0\equiv2n,\qquad n=j_{\max}+l+1\;(\text{principal quantum number}).\]

  • \(\rho_0=2n\) gives the Bohr energies: \[E_n=-\frac{m}{2\hbar^2}\Big(\frac{e^2}{4\pi\epsilon_0}\Big)^2\frac{1}{n^2}=\frac{E_1}{n^2},\qquad E_1=-13.6\ \mathrm{eV}.\]

  • \(k=\dfrac{1}{an}\) with the Bohr radius \(a=\dfrac{4\pi\epsilon_0\hbar^2}{me^2}=0.529\times10^{-10}\) m; \(\rho=\dfrac{r}{na}\).

  • \(v(\rho)\) is a polynomial of degree \(n-l-1\) — an associated Laguerre polynomial; \(n=1,2,3,\ldots\), \(l=0,1,\ldots,n-1\), \(m=-l,\ldots,l\): \[\psi_{nlm}=\sqrt{\Big(\frac{2}{na}\Big)^3\frac{(n-l-1)!}{2n\,(n+l)!}}\;e^{-r/na}\Big(\frac{2r}{na}\Big)^lL_{n-l-1}^{2l+1}\Big(\frac{2r}{na}\Big)Y_l^m(\theta,\phi).\]

First few radial functions

  • \(R_{10}=2a^{-3/2}e^{-r/a}\);   \(R_{20}=\dfrac{1}{\sqrt2}a^{-3/2}\Big(1-\dfrac{r}{2a}\Big)e^{-r/2a}\);   \(R_{21}=\dfrac{1}{\sqrt{24}}a^{-3/2}\dfrac ra\,e^{-r/2a}\).

Figure Figure Figure

Effective potential, ground-state and ionization energy

  • \(V_{\rm eff}=\dfrac{l(l+1)\hbar^2}{2mr^2}-\dfrac{e^2}{4\pi\epsilon_0r}\); bound states have \(E<0\).

  • Ground state \(E_1=-13.6\) eV; ionization energy \(E_s=E_f-E_i=0-(-13.6)=13.6\) eV.

  • Hydrogen-like ion of charge \(Z\): \(E_n=-13.6\,\dfrac{Z^2}{n^2}\) eV, \(a\to a/Z\).

Properties of the radial functions

  • \(R_{nl}\sim r^l\) for small \(r\); decays exponentially at large \(r\).

  • \(R_{nl}\) has \(n-l-1\)

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