- 24,488
- 15,057
I'm not familiar with measurements of the ionization energies. Of course, you have to define the choice of the "zero point" of you energies you measure since what you measure are always energy differences.
What is a "q-observable"?
It's of great importance to understand that the Hamiltonian in general is not gauge invariant and not an observable. That's so already in classical physics when using the Hamilton formulation of the action principle for a particle in an external electromagnetic field. The Hamiltonian contains the electromagnetic potentials and thus is not gauge invariant. For a nice explanation of the issue in the quantum context, see
Donald H. Kobe and Arthur L. Smirl, Gauge invariant formulation of the interaction of electromagnetic radiation and matter, Am. Jour. Phys. 46, 624 (1978)
https://doi.org/10.1119/1.11264
What is a "q-observable"?
It's of great importance to understand that the Hamiltonian in general is not gauge invariant and not an observable. That's so already in classical physics when using the Hamilton formulation of the action principle for a particle in an external electromagnetic field. The Hamiltonian contains the electromagnetic potentials and thus is not gauge invariant. For a nice explanation of the issue in the quantum context, see
Donald H. Kobe and Arthur L. Smirl, Gauge invariant formulation of the interaction of electromagnetic radiation and matter, Am. Jour. Phys. 46, 624 (1978)
https://doi.org/10.1119/1.11264