How do we know that the atomic orbital angular momentum magnitude is sqrt(l(l+1))ℏ, where ℏ = h//2pi?

This is asked for @Saran V.

1 Answer
Jan 28, 2018

What we will show is that overbrace(hatL^2)^("operator")Y_(l)^(m_l)(theta,phi) = overbrace(l(l+1)ℏ^2)^"eigenvalue"Y_(l)^(m_l)(theta,phi).


Consider a spherical harmonic wave function Y_(l)^(m_l)(theta,phi), where l is the orbital angular momentum quantum number and m_l is the magnetic quantum number.

Its general formula for a hydrogen atom is very difficult to use to obtain eigenvalues, so we will take some example wave functions:

Y_(0)^(0)(theta,phi) = Y(s) = 1/2sqrt(1/pi)
Y_(1)^(0)(theta,phi) = Y(p_z) = 1/2sqrt(3/pi)costheta
Y_(2)^(0)(theta,phi) = Y(d_(z^2)) = 1/2sqrt(5/pi)(3cos^2theta - 1)

The orbital angular momentum is L, and the known eigenvalue relates to hatL^2, the squared orbital angular momentum operator.

That is, the value of l arises when we operate on Y using the hatL^2 operator:

hatL^2 = -ℏ^2[1/(sintheta)(del)/(del theta)(sintheta (del)/(del theta)) + 1/(sin^2theta)(del^2)/(delphi^2)]

where theta is the angle from the z axis down to the xy plane, and phi is the azimuthal angle, counterclockwise from the x axis on the xy plane.

![https://upload.wikimedia.org/](useruploads.socratic.org)

What we expect is to get eigenvalues of:

color(green)(hatL^2)Y(s) = overbrace(color(green)(0ℏ^2))^("eigenvalue")Y(s), since 0(0+1)ℏ^2 = 0

color(green)(hatL^2)Y(p_z) = overbrace(color(green)(2ℏ^2))^("eigenvalue")Y(p_z), since 1(1+1)ℏ^2 = 2ℏ^2

color(green)(hatL^2)Y(d_(z^2)) = overbrace(color(green)(6ℏ^2))^"eigenvalue"Y(d_(z^2)), since 2(2+1)ℏ^2 = 6ℏ^2

where |L| then corresponds to the square root of the eigenvalue of hatL^2.

And we would see that s orbitals (and hydrogen atom) have no orbital angular momentum (eigenvalue 0), and they are therefore spheres.

Let's take the most nontrivial example, as if it works out, there is no way it could be a coincidence. Plug it in first:

color(blue)(hatL^2) Y(d_(z^2)) = -ℏ^2[1/(sintheta)(del)/(del theta)(sintheta (delY(d_(z^2)))/(del theta)) + 1/(sin^2theta)(del^2Y(d_(z^2)))/(delphi^2)]

= -ℏ^2[1/(sintheta)(del)/(del theta)(sintheta (del)/(del theta)(1/2sqrt(5/pi)(3cos^2theta - 1))) + cancel(1/(sin^2theta)(del^2)/(delphi^2)(1/2sqrt(5/pi)(3cos^2theta - 1)))^(0)]

Now what we want to do is operate on the function, and get the SAME function back when we are all done.

The first derivative of 3cos^2theta - 1 with respect to theta is -6sinthetacostheta, and the second derivative with respect to phi is 0:

= -ℏ^2[1/(sintheta)(del)/(del theta)(1/2sqrt(5/pi)sintheta (-6sinthetacostheta))]

Now we simplify this a bit:

= 6ℏ^2cdot 1/2sqrt(5/pi)[1/(sintheta)(del)/(del theta) (sin^2thetacostheta)]

The first derivative of sin^2thetacostheta with respect to theta is -sin^3theta + 2sinthetacos^2theta, giving:

= 6ℏ^2cdot 1/2sqrt(5/pi)[1/cancel(sintheta)(-sin^(cancel(3)^(2))theta + 2cancel(sintheta)cos^2theta)]

= 6ℏ^2cdot 1/2sqrt(5/pi)[(-sin^2theta + 2cos^2theta)]

= 6ℏ^2cdot 1/2sqrt(5/pi)[(-sin^2theta + 2cos^2theta + cos^2theta - cos^2theta)]

= 6ℏ^2cdot 1/2sqrt(5/pi)[3cos^2theta - (sin^2theta + cos^2theta)]

= color(blue)(6ℏ^2) cdot overbrace(1/2sqrt(5/pi)[3cos^2theta - 1])^(Y(d_(z^2))

And our eigenvalue is indeed 6ℏ^2.

If you did this on other Y_(l)^(m_l)(theta,phi) functions, you would find the pattern l(l+1) ℏ^2 works. Taking the square root gives the magnitude of the orbital angular momentum, |L|.

Therefore,

color(blue)(|L| = sqrt(l(l+1)) ℏ)

You should try this on Y_(0)^(0) and Y_(1)^(1) to get the idea.