Lecture 20B: Schrdinger eqn.

for the atom

The Bohr Model, applicability, pros and cons Choosing a coordinate system Converting the Schrdinger equation The Coulomb potential Solving the Schrdinger equation Separation of variables The and equations Legendre polynomials The R equation The radial wavefunctions Spherical harmonics
PHYS2040 Lecture 20B Schrdinger eqn. for the atom PHYS 2040 Quantum Updated:Physics 19/5/2008 8:54 PM

The Bohr model

Last week we developed Bohrs model of the atom, where electrons orbit a positive nucleus in orbits that have an angular momentum quantized in integer multiples of h. We found that this gives us allowed radii and energy levels:

0 h 2 2 a0 2 rn = n = n 2 Z mZe
where:

(19.6)

Z 2 E0 mZ 2 e 4 En = = 2 2 2 2 n 8 0 h n

(19.11)

a0 = 0h2/me2 = 0.53 is called the Bohr radius E0 = e2/80r0 = me4/80h2 = 13.6eV is called the Rydberg energy and n is the quantum number of the electrons orbit.

1. 2.

Bohrs model of the atom explained two key experimental findings when it was developed, these were: Rutherfords experiments showing unexpectedly high backscattering of -particles (4He2+ ions) from a thin gold foil (like a bullet bouncing of tissue paper). Experiments on the optical emission and absorption spectra of gases showing that the wavelengths of the spectral lines depends only on a single constant and two integers (i.e., the Rydberg-Ritz equation)

1 1 = R 2 2 m n 1
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(19.14)

Applicability, pros and cons

1. 2. 3. 4. Bohrs model works remarkably well for one electron atoms, especially if you correct for the finite mass of the nucleus (see E&R). Some examples are: The Hydrogen atom one electron orbiting one proton. The Helium He+ ion one electron orbiting two protons and two neutrons. The Lithium atom a helium atom with an electron orbiting it and so on through the group I elements. The Beryllium Be+ ion and so on through the group II elements. It gets systematically less accurate as you work your way down that list (and towards higher mass), and it fails entirely for most of the periodic table, but its a good start. Some pros and cons of Bohrs model: Pros: Its simple, very simple, but gives remarkably accurate answers for simple systems. Cons: Its a little too simple, so it only works for simple systems. Its also purely radial, which means it cant describe the angular distribution of things like chemical bonds
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Applicability, pros and cons

Cons: Its a little too simple, so it only works for simple systems. Its also purely radial, which means it cant describe the angular distribution of things like chemical bonds

Chemistry at the time had well established the asymmetry of certain atoms in forming chemical bonds. This suggests that the Bohr model is not really wrong (after all, it works for simple cases), but its not a complete model of how the atom works. Today, were going to start on the next step, applying the Schrodinger equation to the Hydrogen atom, with the intention of getting a better model of the atom.
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Choosing a coordinate system

An important thing in physics is setting up a problem properly. If you do it right, a problem is rather easy, if you do it wrong, the problem is near impossible. So far, weve been using the Cartesian or rectangular coordinate system (x,y,z) but this is a poor choice for a problem such as this one, where we have a clear potential for spherical symmetry (i.e., a particle orbiting another in 3 dimensions). Hence, from here forth, we will use spherical coordinates (r,,).

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Converting the Schrdinger equation

So far, weve only dealt with the Schrdinger equation in one-dimension, it has the form:

h 2 d 2 ( x) + V ( x) ( x) = E ( x) 2 2m dx

(10.1)

The energies in different directions add directly as scalars, so writing the Schrdinger equation in three-dimensions is pretty easy:

h2 d 2 d2 d2 2 + 2 + 2 ( x, y, z ) + V ( x, y, z ) ( x, y, z ) = E ( x, y, z ) 2m dx dy dz

(19A.1)

It is often convenient to write this as:

h2 2 ( x, y, z ) + V ( x, y, z ) ( x, y, z ) = E ( x, y, z ) 2m
where:

(19A.2)

d2 d2 d2 = 2+ 2+ 2 dx dy dz
2

(19A.3)

which is called the Laplacian operator, or del-squared, in rectangular coordinates.

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Converting the Schrdinger equation

We now need to convert the 3D Schrdinger equation (Eqn 19A.2) into spherical coordinates. The main thing we need to do is convert the Laplacian to spherical coordinates. You should be able to do this (its just the chain rule, applied numerous times if you want to work through it, see Appendix M of Eisberg and Resnick). The result is:

h2 2 (r , , ) + V (r , , ) (r , , ) = E (r , , ) 2m
where:

(19A.4)

1 2 1 1 2 = 2 r + 2 sin + 2 2 r r r r sin r sin 2

2

(19A.5)

which is called the Laplacian operator, or del-squared, in spherical coordinates.

Right now, it might look like Im just making the problem more complicated, but thats not true, its just a complicated problem over all. If I stayed in rectangular coordinates then sure, 2 would look nicer, but Id end up with a lot of sin/cos terms later on, I wont be able to perform the separation of variables step (coming up) and I would have a very hard time comparing the results directly to Bohrs model also.
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The Coulomb potential

Of course, the next step is the potential. There is only one force on the electron in this problem the Coulomb attraction between the negative electron and the positive nucleus. Because this depends only on the separation between the charges, F and hence V are purely radial (no terms in and ). So, as a force:

r ( e ) (+ Ze ) r F = 2 4 0 r
and therefore as a potential:

(19A.6)

r Ze 2 dr = V (r ) = F .r 4 0 r

(19A.7)

Note that there is a Z in here. Z is the atomic number (each element has a number of protons and hence a nucleus charge equal to its atomic number) and it allows us to make our model applicable to atoms beyond hydrogen, but This problem still only works for one electron (if we have more, they can interact with each other and we need to account for that), hence the single negative charge. But youll see later, we can still infer results about more complex atoms despite this limitation.
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Solving the Schrdinger equation

So now we have the complete Schrdinger equation for the one-electron atom (with Z protons in it):

h2 2 Ze 2 (r , , ) + (r , , ) = E (r , , ) 2m 4 0 r
where:

(19A.8)

1 2 1 1 2 = 2 r sin + 2 + 2 2 r r r r sin r sin 2

2

(19A.5)

Solving it is no easy task, but there is one aspect that makes it infinitely easier. This is that the potential V depends only on r, it has no terms in or . This means we can use the same trick we did earlier in developing the time-independent Schrdinger equation Separation of variables.

(r , , ) = R(r )( ) ( )

(19A.9)

In other words, the wavefunction solution to Eqn. 19A.8 is composed of the product of three separate functions, each of which is an independent function of one of the three spatial variables (n.b., this is the main reason why we switch to spherical vars.)
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Separation of variables

If we now substitute our separated solution (Eqn 19A.9) into Eqn 19A.8, and carry out the three derivatives:

R = r r
we get:

= R

2 2 = R 2 2

(19A.10)

h2 2m

d 2 dR R d d R d 2 Ze 2 R = ER + 2 2 sin r + 2 2 2 d r sin d 4 0 r r dr dr r sin d

And if we then multiply both sides by 2mr2sin2/Rh2:

1 d 2 sin 2 d 2 dR sin d d 2m 2 2 = sin 2 r sin [E V (r )] (19A.11) r d 2 dr d d R dr h

Notice that the left side has no terms in r and , and the right no terms in . Hence we can separate this into two equations, just like we did last time in lecture 10. The common value must be a constant, and well designate it as ml2 for reasons well see later on.
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Separation of variables

And so we have our first of three equations:

2 2 = m l 2
and:

(19A.12)

sin 2 d 2 dR sin d d 2m 2 2 2 [ ] sin r sin E V ( r ) = m r l h2 d d R dr dr

we can divide through by sin2, and then collect terms as follows:

(19A.13)

d d ml 1 d 2 dR 2m 2 1 + = r r E V r + 2 [ ] ( ) sin 2 sin d R dr dr h d sin

2

(19A.14)

And now again we can use the same trick! The equation on the left is independent of and the equation on the right is independent of r, and so we can separate them and assume both sides are equal to a constant, which we will designate as l (l + 1), again for reasons that we will soon see. So now we have three equations from which to get three unknown solutions R(r), () and (), these are:
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The three equations

2 2 = m l 2
1 d d ml + 2 = l (l + 1) sin sin d d sin
2

(19A.12)

(19A.15)

1 d 2 dR 2m R [ ] r + E V ( r ) R = l ( l + 1 ) r 2 dr dr h 2 r2

(19A.16)

Note that with the last one, Ive multiplied through by R/r2 for convenience. In solving these equations, we will find that the equation for () has acceptable solutions only for certain values of ml. Using these values in the equation for (), we find that this equation has acceptable solutions only for certain values of l. And finally, using these values in the equation for R(r), this equation is found to have acceptable solutions only for certain values of the total energy E. In other words, the energy of the atom is quantised. And now for the downhill run, lets solve these equations one by one
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The equation
2 2 = m l 2
(19A.12)

This ones a piece of cake, weve been solving it (or its kind at least) for weeks, the solution is: (19A.17) ( ) = e iml
ml

The subscript ml is used to identify the specific form of an acceptable solution. Now this obeys the same rules as any wavefunction, namely that its finite, continuous and single-valued. Now = 0 and = 2 are actually the same angle (in fact it goes deeper than that, as an angle is modulo 2) therefore:

(0) = (2 )
which means ml must be an integer:

or

eiml 0 = eiml 2
ml = 0,1,2,3,...

(19A.18)

ml = ...,3,2,1,0,1,2,3,...

or

(19A.19)

The quantum number ml is called the magnetic quantum number.

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The equation
d ml 1 d + 2 = l (l + 1) sin sin d d sin
2

(19A.15)

This equation is not so easy to solve, so I wont go into it deeply. The solution process is similar to that used in the simple harmonic oscillator. If youre interested in seeing it all, Appendix N in Eisberg and Resnick discusses it in full detail. Firstly, the solutions that are found to be acceptable (i.e., remain finite) are only obtained if the quantum number l (called the azimuthal quantum number) is equal to one of the integers:

l = ml , ml + 1, ml + 2, ml + 3,...

(19A.20)

And the wavefunction solution has the form:

l ,ml ( ) = sin

ml

Fl , m (cos )
l

(19A.21)

where Fl,m(cos ) are called Legendre polynomials, which look like

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Legendre polynomials

Note well, youll sometimes see these with different notation, sometimes P, sometimes F, keep your eyes peeled .

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The R equation
1 d 2 dR 2m R [ ] r + E V ( r ) R = l ( l + 1 ) r 2 dr dr h 2 r2
(19A.16)

Same situation for R, the solution is involved and you can find it in detail in Appendix N of Eisberg and Resnick if you want to see it. But ultimately, we find bound-state solutions that are acceptable (remain finite) only if the constant E (the total energy) has one of the values En, where:

Z 2 E0 mZ 2 e 4 = 2 En = 2 2 2 (4 0 ) 2h n n

(19A.22)

And remarkably, E1 = 13.6eV! In other words, we have exactly the same energy eigenvalues that we got in Bohrs model. The quantum number n (called the principal quantum number) is given by:

n = l + 1, l + 2, l + 3,...

(19A.23)

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A quick look at the energy levels

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The radial wavefunctions

And the R wavefunction solution has the form:

Zr Zr na0 Zr Rn ,l (r ) = e a Gnl a 0 0
where Gn,l(Zr/a0) are polynomials

(19A.24)

Note also that a0 = 40h2/me2 = 0.53 is the Bohr radius, the same characteristic radius that we found in the Bohr model.

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Spherical harmonics

And so now weve finished the mathematical aspect of the problem. Before I recap the solution, Ill make a slight tweak to how we present the wavefunctions:

n ,l ,m (r , , ) = Rn ,l (r )l ,m ( ) m ( ) = Rn ,l (r )Yl ,m ( , )
l l l l

(19A.25)

where we combine the angular terms to create what are known as spherical harmonics Y(,):

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Summary of the solutions

So ultimately, we have eigenfunctions that look like:

n ,l , m ( r , , ) =
l

Zr Zr na0 Zr ml iml G e sin F (cos ) e l , ml nl a a 0 0

Z 2 E0 mZ 2 e 4 = 2 En = 2 2 2 (4 0 ) 2h n n

(19A.26)

with energy eigenvalues: (19A.22)

and three sets of quantum number relations:

n = l + 1, l + 2, l + 3,...

l = ml , ml + 1, ml + 2, ml + 3,...

ml = 0,1,2,3,...

which determine what are acceptable solutions to the Schrdinger equation.

Right now, youre probably feeling very mathed out. So well leave it there for now, and in the next lecture, we will have take a more pictorial, physical look at what these solutions really mean.
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Summary

The Bohr model works very well in a few very simple cases, and reasonably well in other cases, but its a very simple model so its predictive power is rather limited. In this lecture, we look to (a) test it and (b) extend it by using the Schrdinger equation as a parallel approach to modeling the one-electron atom. (n.b., proper modeling of multielectron atoms needs some more advanced techniques/considerations). For the atomic Schrdinger equation, the potential is due to the Coulomb attraction between a nucleus of charge +Ze and an electron of charge e, hence V(r) = Ze2/40r. This problem is best dealt with in spherical coordinates, mainly because the potential in this case is spherically symmetric. This then allows us to use separation of variables to turn a really hard problem into three slightly less hard problems. This is a classic approach in physics, which is why I really wanted to demonstrate it how a smart choice in setting up the problem can yield good results. We get three equations that give us eigenfunction solutions R(r), () and (), which have acceptable solutions for certain values of three quantum numbers n,l and ml. Remarkably, the energy eigenvalues for this problem En = 13.6eV/n2 are exactly the same as those in Bohrs model, which demonstrates that the two theories in principle agree. As well see next week, the Schrdinger model explains some things that Bohrs model cant, namely the geometry of chemical bonds in certain molecules.

= Brooks/Cole - Thomson

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