Energy and accuracy
Chapter focus
What energy will we calculate, and how accurate must the result be?
Learning objectives
After completing this chapter, you will be able to:
Identify the electronic and nuclear contributions to the fixed-geometry ground-state energy reported in this tutorial.
Explain why small energy errors can cause large errors in predicted equilibria and rates.
Explain why each energy comparison requires a clearly defined reference.
Identify the main approximations that affect the final energy estimate.
Lab notebook assignment
Complete the Calculation goal and reference plan section of the lab notebook. Record the molecular system, target quantity, \(1\ \mathrm{m}E_{\mathrm{h}}\) teaching target, and reference used to evaluate that target. For each comparison field, state what changes, what remains fixed, and what the resulting difference will measure; later chapters add the numerical values. This entry defines the criteria you will use to interpret every later result.
The energy reported in this tutorial
The tutorial introduction introduced the ground-state eigenvalue of the electronic Hamiltonian for fixed nuclear positions. The quantity ultimately reported by this tutorial is the corresponding fixed-geometry total energy,
where \(\mathbf{R}\) denotes the fixed nuclear coordinates. The electronic contribution includes the electron kinetic energy, electron–nucleus attraction, and electron–electron repulsion. The nuclear contribution is the repulsion among the fixed nuclei. Mapping the problem to qubits explains how these contributions are tracked when the molecular Hamiltonian is represented on qubits.
Which contributions make up the fixed-geometry total energy reported by this tutorial?
The fixed-geometry total energy is the sum of the electronic energy and the repulsion energy among the fixed nuclei.
QDK/Chemistry reports molecular energies in hartree, with symbol \(E_{\mathrm{h}}\). One millihartree, written \(1\ \mathrm{m}E_{\mathrm{h}}\), is \(10^{-3}\ E_{\mathrm{h}}\), approximately \(2.6255\ \mathrm{kJ\,mol^{-1}}\) using the 2022 CODATA constants [MNT25].
Energy differences require context
A basis set is a finite collection of mathematical functions used to represent molecular orbitals in a calculation. Describing the molecule explains how basis sets are constructed and used. Chemically meaningful questions usually compare energies calculated under a consistent set of choices, including geometry, basis set, and electronic-structure method. Examples include the energy difference between two molecular geometries, the reaction energy between products and reactants, and the barrier between a reactant and a transition state. In a chemical reaction, starting species called reactants transform into resulting species called products. A transition state is a high-energy molecular arrangement along this transformation; its energy relative to the reactants defines the reaction barrier. Changing the model or numerical method between the two calculations can make the difference difficult to interpret. If several choices change at once, their effects are combined in one number, so the difference cannot be attributed to a particular geometry, basis set, or method.
Why energy accuracy matters
Accurate electronic energies are necessary inputs to predictions of chemical equilibria and reaction rates, but they are not sufficient by themselves. At constant temperature and pressure, these predictions depend on Gibbs free-energy differences that also include zero-point energy, thermal, entropic, and environmental contributions. This tutorial calculates only the fixed-geometry electronic and nuclear components of the energy; it does not calculate a free energy.
Why does an accurate electronic energy not, by itself, determine an equilibrium constant or rate?
Electronic and nuclear energies are only some of the contributions to a free energy. Zero-point, thermal, entropic, and environmental contributions can also affect an equilibrium constant or reaction rate.
When an electronic-and-nuclear energy difference contributes to a free-energy difference, any uncanceled error in that component also contributes to the free-energy error. The dimensionless equilibrium constant \(K\) is related to the standard reaction Gibbs free energy \(\Delta G^\circ\) by
where \(R\) is the molar gas constant and \(T\) is the absolute temperature. Similarly, the Eyring equation relates a rate constant \(k\) to the activation Gibbs free energy \(\Delta G^\ddagger\):
Because both relations are exponential, a small free-energy error can substantially change the predicted equilibrium constant or rate. At \(298.15\ \mathrm{K}\), a \(1\ \mathrm{m}E_{\mathrm{h}}\) error can change the prediction by a factor of approximately \(2.88\) if all other contributions are exact. An error of approximately \(2.17\ \mathrm{m}E_{\mathrm{h}}\) produces a factor of ten.
Why can a small free-energy error cause a large error in a predicted equilibrium constant or reaction rate?
Equilibrium constants and reaction rates depend exponentially on reaction and activation free-energy differences. A small error in a free-energy difference can therefore multiply the predicted equilibrium constant or rate by a large factor.
Accuracy, precision, and other definitions
An energy estimate is accurate only in relation to a stated reference value for the same quantity.
- Accuracy
Closeness to the reference.
- Precision
The spread among repeated estimates under the same conditions.
- Resolution
The smallest energy interval that the chosen numerical representation can distinguish.
- Uncertainty
The range of values plausibly consistent with the available information.
A calculation can be precise but inaccurate, or have fine resolution without a small uncertainty.
The teaching target
This tutorial uses \(1\ \mathrm{m}E_{\mathrm{h}}\) as a teaching target for the absolute difference between the final QPE total energy and a classical reference energy for the same Hamiltonian. This target concerns accuracy relative to the selected-space classical reference; resolution, precision, and uncertainty describe separate properties of the calculation. Meeting this target shows that the quantum algorithm reproduced its classical reference to the requested tolerance. It does not show that the molecular model agrees with experiment, nor does it remove errors from the geometry, basis set, electronic-structure model, or omitted free-energy contributions.
Where approximations enter
Different stages introduce different approximations or uncertainties. For example:
The fixed molecular geometry and Born–Oppenheimer approximation define the physical model considered by the tutorial.
A finite basis set restricts the one-electron functions used to describe the molecule.
Hartree–Fock limits the wavefunction to one determinant, while the selected active-space model fixes occupations outside the active orbitals. These restrictions introduce model error relative to full configuration interaction (FCI) in the same finite orbital basis.
Hamiltonian time evolution is approximated when the quantum circuit is constructed.
Finite phase resolution and measurement sampling limit the reported QPE estimate.
Each approximation is introduced where it first enters the calculation, and the corresponding comparison is recorded before proceeding.