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Semidiffuse states of diatomic molecules: Configuration interaction studies of the lowest 2 Σ + and 2 Δ states of NS, SiF, and CCl
Author(s) -
Karna S. P.,
Grein F.
Publication year - 1986
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560290415
Subject(s) - rydberg formula , valence (chemistry) , atomic physics , chemistry , diatomic molecule , configuration interaction , wave function , rydberg state , ab initio , molecule , atomic orbital , state (computer science) , excited state , physics , ion , ionization , quantum mechanics , electron , organic chemistry , algorithm , computer science
It has been shown by ab initio configuration‐interaction methods that the lowest 2 Σ + states of NS and SiF are ‘semidiffuse’ states, like the B 2 Σ + state of PO. The lowest 2 Σ + state of CCl also appears to be semidiffuse, although here the situation is not so clear. Semidiffuse states require diffuse orbitals in the wavefunction, but they are not Rydberg states. The second 2 Σ + state of each molecule is shown to be the lowest ns Rydberg state, whereas the third 2 Σ + state is a valence state for NS and CCl, and a 4 po Rydberg state for SiF. The lowest 2 δ state of each molecule derives from the 7σ → 3π valence configuration. Comparison with available experimental information shows, in general, good agreement.