Rydberg, theory

Choppin, G. Rydberg, J. "Nuclear Chemistry. Theory and Applications" Pergamon Press London, 1980. 

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 ... 

Such long lifetimes are puzzling in view of the well-known n3 scaling of Rydberg state lifetimes observed from linewidths of resolvable series and predicted by theory. The n3 scaling derives from a fundamental property of Rydberg states. The normalization factor in the radial part of the Rydberg orbital scales as n 3/2. Thus... 

The book contains very little original material, but reviews a fair amount of forgotten results that point to new lines of enquiry. Concepts such as quaternions, Bessel functions, Lie groups, Hamilton-Jacobi theory, solitons, Rydberg atoms, spherical waves and others, not commonly emphasized in chemical discussion, acquire new importance. To prepare the ground, the... 

We can divide the NAOs into the natural minimal basis (NMB), consisting of only the formal core and valence NAOs of simple bonding theory, and the natural Rydberg basis (NRB), consisting of everything else. With this partitioning, Eq. (3.24a) is expressed as... 

Choppin, G.R. and Rydberg, J. (1983) Nuclear chemistry - its theory and applications, Pergamon Press, UK. 

Keywords electron-capture dissociation electron-transfer dissociation electron transfer Rydberg orbital Landau-Zener theory... 

In the studies our group has undertaken [3h-3w] to date, we used LZ theory to estimate the probabilities P for an electron being transferred from such a Rydberg orbital to an SS cr or amide n orbital. In Figure 5 we show actual data from such a study on the H3C—S—S—(CH2)3—NH " model compound. 

By using a full panoply of theory—time-dependent density functional theory and CASSCF and CASMP2 ab initio methods—the states and potential-energy surface features associated with the dynamics were uncovered. The high-energy excitation of acetone gives several excited Rydberg states that reach the S2( , 3i) surface in... 

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