Rydberg electron energy levels

Calculate the electron energy levels of the hydro n atom from a knowledge of the Rydberg constant... 

The atomic spectrum of the hydrogen atom is described in Chapter 1. Its study, and that of other atomic spectra, provide much evidence for the quantization of electronic energy levels. The energy levels of the single electron in the hydrogen atom are represented by equation (2.1), which is derived from the Rydberg equation (1.16) in Chapter 1 ... 

These energy levels have exactly the form suggested spectroscopically, but now we also have an expression for S( in terms of more fundamental constants. When the fundamental constants are inserted into the expression for the value obtained is 3.29 X 10,s Hz, the same as the experimental value of the Rydberg constant. This agreement is a triumph for Schrodinger s theory and for quantum mechanics it is easy to understand the thrill that Schrodinger must have felt when he arrived at this result. A very similar expression applies to other one-electron ions, such as He1 and even C5+, with atomic number Z ... 

The existence of outsized hydrogen atoms was inferred early on from the observation that 33 terms of the Balmer series could be observed in stellar spectra, compared to only 12 in the laboratory [58]. More recently [59] Rydberg atoms have been produced by exciting an atomic beam with laser light. When the outer electron of an atom is excited into a very high energy level, it enters a spatially extended orbital which is far outside the orbitals... 

Figure 9.1. Energy level diagram for hydrogen molecule, H2, and separated atoms H R = 00) and He R = 0). R = the Rydberg constant = 13.6057 eV = 0.5 a.u. (atomic unit of energy). Value from ionization potential of He (Is 2p P). Value from ionization potential of H2. The experimental ionization potentials are quite precise but for systems containing more than one electron their interpretation in terms of orbital energies is an approximation.

When a) l/n3, the field required for ionization is E = 1/9n4, and as a> approaches l/n3 it falls to E=0.04n. These observations can be explained qualitatively in the following way. At low n, so that a> 1/n3, the microwave field induces transitions between the Stark states of the same n and m by means of the second order Stark effect. With only a first order Stark shift a state always has the same dipole moment and wavefunction, as indicated by the constant slope dW/d of the energy level curve. Thus when the field reverses, — — , the Rydberg electron s orbit does not change. With a second order Stark shift as well, the slope dW/d is not the same at E and —E, and as a result the dipole moment and wavefunction are not the same. If the field is reversed suddenly a single Stark state in the field E is projected onto several Stark states of the same n and m when E — - E. Since all the Stark states of the same n make transitions among themselves they ionize once the field is adequate to ionize one of them, the red one, at E = 1/9n4 for m n. 

In the first two chapters we have seen that the Na atom, for example, differs from the H atom because the valence electron orbits about a finite sized Na+ core, not the point charge of the proton. As a result of the finite size of the Na+ core the Rydberg electron can both penetrate and polarize it. The most obvious manifestation of these two phenomena occurs in the lowest states, which are substantially depressed in energy below the hydrogenic levels by core penetration. Core penetration is a short range phenomenon which is well described by quantum defect theory, as outlined in Chapter 2. 

Ba Rydberg energy levels (—) and continua (///) obtained by adding the second valence electron to these Ba+ levels. The horizontal arrows show the possible interactions between channels associated with different ion levels. Interactions with other bound states lead to series perturbations while interactions with continua lead to autoionization. 

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