Quantum Mechanics for Engineers © Leon van Dommelen

Next: A.18 The energy-time uncertainty relationship

A.17 The virial theorem

The virial theorem relates the expectation kinetic energy of a quantum system to the potential. That is of theoretical interest, as well as important
for computational methods like “density functional theory.”

Consider a quantum system in a state of definite energy . In other words, consider a quantum system in a stationary state. It does not have to be
the ground state. The quantum system will be assumed to be in infinite space.

To keep it simple, for now assume that there is a single particle with position vector in a potential . That covers our previous examples of
the harmonic oscillator and the hydrogen atom.

Then the virial theorem relates the expectation kinetic energy to the potential as follows:

(A.75)

(Recall that nabla, , is just the multi-dimensional derivative .) The above formula can be very useful.

For example, consider the harmonic oscillator. There

so in Cartesian coordinates

Then according to the virial theorem . So the expectation kinetic energy and the expectation potential energy are the same. Compute
whichever is easiest, or just take half of the total energy if you know it.

Also consider the hydrogen atom. There

so in polar coordinates

Then according to the virial theorem the expectation potential energy is minus twice the expectation kinetic energy. And their sum, the total energy
, is then minus the expectation kinetic energy. In short, and with negative.

The virial theorem does not apply to the particle in a pipe, as that particle is in a bounded space. (You can assume infinite space if you take the
potential infinite outside the pipe, but obviously by itself that does not help much. You could assume infinite space with a potential

if you then take the limit to get infinite potential outside the pipe and zero inside. That gives the correct but trivial result that all the energy
is kinetic.)

But the virial theorem does apply to any number of particles, not just to one. Just sum over all the particles:

where i is the particle number.

For example, consider the hydrogen molecule, where there are four particles, two protons and two electrons. Here

where is if particle is a proton and if it is an electron. Like for the simple hydrogen atom,

so the total expectation potential energy of the system is still twice the total energy and the total kinetic energy is still minus . And this contin-
ues to hold for much bigger systems of nuclei and electrons, which is why it is of interest for computational methods.

In some computations you might need to assume that the electrons are in a state of definite energy, like in the ground state, but the nuclei are not.
In such computations the nuclei are at an assumed position and you will only compute the state of the electrons. So the summation in

now extends only over the electrons. But this summation does includes potentials of the electrons due to the attraction by the nuclei, and those
terms are no longer equal to minus the corresponding potentials. You may need to evaluate these terms explicitly. But that is not too bad, as these
potentials are now known functions of the individual electron positions only. The difficult term, due to the electron-electron interaction, is still given
by minus the corresponding potential.

Finally, you might wonder where the virial theorem comes from. Well, one way to prove the virial theorem, as found in quantum textbooks and on
Wikipedia, is to work out the commutator in

using the formulae in chapter 4.5.4, to give

and then note that the left hand side above is zero for stationary states, (in other words, for states with a precise total energy). This follows the
classical way of deriving the classical virial theorem, but requires a messy purely mathematical derivation. The theorem then pops up out of the
complex mathematics without any plausible physical reason why there would be such a theorem in the first place.

The original derivation by Fock in 1930 is much more physically appealing and more instructive. The idea is to slightly stretch the given quantum
system: replace every position coordinate coordinate by a slightly larger one . Here is assumed to be a vanishingly small num-
ber. We are interested in what the expectation potential and kinetic energy are in this slightly stretched system.

First however, recall that the square magnitude of the wave function gives the probability of that state, and that all probabilities must integrate to-
gether to 1, certainty. Phrased differently, the expectation value of one must be one; , what else? But clearly, if you integrate the same
square wave function magnitude over a slightly larger domain, you will get a value slightly greater than one. This problem is easily fixed, however,
by multiplying the wave function in the stretched system by a suitable constant slightly less than one. Then too. (The precise value of the
constant depends on the number of particles and is not important.)

Next, the expectation kinetic energy consists of terms like times because of the form of the kinetic energy operator. Because
of the stretching of the coordinate in the bottom of the derivative, each of these terms changes by a factor , so

For the potential energy we can use a linear Taylor series to figure out how it changes:

where in the right hand side and its derivatives are evaluated at . From that

From the above expressions, it is seen that compared to the unstretched system, in the stretched system the sum of expectation kinetic and po-
tential energies is different by an amount

But, as described in {A.7}, if you mess up an energy wave function by an amount of order , the expectation energy should only be messed up by
an amount proportional to , not . (In brief, the amounts of the other energy eigenfunctions found in the messed up wave function are propor-
tional to . However, the probabilities of their energies are proportional to the squares of the amounts.) So the factor between parentheses in the
expression above must be zero, and that is the virial theorem.

Next: A.18 The energy-time uncertainty relationship

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