Rydberg molecular

Simons, J., Gutowski, M. Double-Rydberg molecular anions. Chem. Rev. 1991, 91, 669-77. 

When aos are combined to form mos, core, bonding, nonbonding, antibonding, and Rydberg molecular orbitals can result. The mos (f>i are usually expressed in terms of the constituent atomic orbitals %a in the hnear-combination-of-atomic-orbital-molecular-orbital (LCAO-MO) manner ... 

The classical trajectory simulations of Rydberg molecular states carried out by Levine ( Separation of Time Scales in the Dynamics of High Molecular Rydberg States, this volume) remind me of the related question asked yesterday by Prof. Woste (see Berry et a]., Size-Dependent Ultrafast Relaxation Phenomena in Metal Clusters, this volume). Here I wish to add that similar classical trajectory studies of ionic model clusters of the type A B have been carried out by... 

The difference between the spin-orbit constants of the main constituent atomic orbital, A(atom, nl), in the Rydberg molecular orbital and that of the molecular Rydberg state, Ar, is due to penetration of the Rydberg MO into the molecular core, i.e., to the contribution of the (n — l) atomic orbital responsible for the orthogonality between the Rydberg MO and the molecular core orbitals. 

H2 molecular beam. The H-atom products were detected by the Rydberg tagging TOF technique using the same scheme described in the last paragraph with a rotatable MCP detector. Figure 4 shows the experimental scheme of the crossed beam setup for the 0(1D) + H2 reactive scattering studies. The scheme used for the H + D2(HD) studies is very similar to that used in the 0(1D) + H2 except that the H-atom beam source is generated from HI photodissociation rather than the 0(1D)-atom beam source from 02 photodissociation. 

The second step in the reaction, dissociation of the Hej Rydberg molecule, is similar to dissociative recombination of He with a free electron. For this reason, Bates73 called this recombination mechanism Rydberg dissociative recombination. It enhances the overall loss rate of free electrons because the stabilization of He2 prevents the return of weakly bound electrons to the population of free electrons. The reaction plays the same role as the reaction of H with H2 that we discussed in Section IV.C. As has been discussed by Bates, the mechanism also provides an explanation for spectroscopic observations of atomic and molecular emissions in helium afterglows. There is direct evidence for the existence of a substantial population of weakly bound electrons in helium afterglows.74 Most likely, the weakly bound electrons are Rydberg electrons in He2 molecules. 

The quality of the TD-DFT results is determined by the quality of the KS molecular orbitals and the orbital energies for the occupied and virtual states. These in turn depend on the exchange-correlation potential. In particular, excitations to Rydberg and valence states are sensitive to the behavior of the exchange-correlation potential in the asymptotic region. If the exchange-correla-... 

Below the photoionisation threshold a core electron in a free molecule can be excited into empty anti-bonding molecular orbitals (m.o. s) as well as into Rydberg states. These transitions are observable as sharp features directly below the corresponding absorption edge (carbon K, oxygen K etc.). Above the... 

Rydberg series were detected in molecular spectra in the early 1930 s, notably by W. C. Price who showed that they arose from the outer electrons. These can usually be fairly well classified in terms of the structure of the molecule, e.g. non-bonding electrons on particular atoms or electrons of double bond systems. Non-bonding electrons give more nearly atomic Rydberg series, with many numbers observable, and correspondingly accurate ionization potentials have been recorded. Most of the earlier measurements belong to this class. 

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