What a learner can do afterwards
- Writes the partition function as a sum over levels and evaluates it for a two-level system
- Sums the vibrational series as a geometric series and states the closed form
- Explains what the limiting values at low and high temperature mean physically
- Separates the total into translational, rotational, vibrational and electronic factors and says why the separation is allowed
1 · Read
Summing the Boltzmann factors over every level of a molecule gives one number that counts how many levels are effectively in use. Each level adds its degeneracy times e to minus its energy over kT, so accessible states add a lot and remote states add almost nothing. Levels that are low and numerous pull the sum up, and a large sum marks a strongly favored state.
With the ground level set to zero energy, a two-level system gives q equal to 1 plus e to minus gap over kT: the ground term of one plus one excited term. If the excited factor is 0.3, q is 1.3. A vibrational ladder of equally spaced levels forms a geometric series, giving q equal to 1 over 1 minus the factor: with a factor of 0.5, q is 2.
Near zero temperature only the ground level counts, so q sinks toward 1, while high temperature lets countless levels contribute. The total separates into translational, rotational, vibrational, and electronic factors multiplied together, which is allowed because those motions are nearly independent. The partition function is the normalising sum of the winning energy sharing, so averages match its values.
To reach bulk properties, take the logarithm of q and multiply by thermal energy: the free energy drops out. One formula gathers every level, and thermodynamics follows by differentiation, which is why the sum is the bridge between molecules and moles.
The partition function sums weighted levels into one count of states in use, and its logarithm opens the door to bulk thermodynamics.
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Where it sits
8 questions wait behind this lesson, each with its answer explained. Every answer feeds the sky: stars light as they are learned, and dim when it is time to come back.