TITLE

The singlet electronic excited states of the F[sub 2] molecule

AUTHOR(S)
Moriyama, H.; Wasada-Tsutsui, Y.; Sekiya, M.; Tatewaki, H.
PUB. DATE
March 2003
SOURCE
Journal of Chemical Physics;3/22/2003, Vol. 118 Issue 12, p5413
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
By using multireference single excitation configuration interaction calculations and multireference single and double excitation CI calculations, we consider the ¹Σ[sup +, sub u]. ¹Π[sub g], and ¹Π[sub u] excited states of the F[sub 2] molecule which lie between 4.3 and 14.1 eV above the ground state. The basis set is composed of 13s, 10p, 7d, and 2f contracted Gaussian-type functions, and covers molecular orbitals spanned by 4s, 4p, and 3d Rydberg orbitals. Of the ¹Σ[sup +, sub u] ¹Σ[sup +, sub u] + states, G is sometimes disregarded, presumably because it is not directly observed by optical measurements, but is inferred from perturbations in the visible and ultraviolet spectra. We find that G ¹Σ[sup +, sub u] arises from the shallow local minimum in the lowest ¹Σ[sup +, sub u] E potential curve, which also has a stable minimum corresponding to the state designated C¹ are Σ[sup +, sub u].The experimental excitation energies (T[sub 0] values) for G ¹Σ[sup + sub u] 12.81-12.87 eV according to electron energy loss spectroscopy, and our theoretical value is 13.06 eV. Agreement between the experiment and the calculation is quite close. The state has a mixed ionic-Rydberg character with an interesting Rydberg portion. The experimental and calculated TO values for C¹Σ[sup +1, sub u] are, respectively, 11.57 and 11.59 eV, suggesting that the present calculation for the state is reliable. Ambiguity found in experimental assignments of the vibrational levels for C ¹Σ[sup +, sub u] is settled here. The ¹Π [sub g] and ¹Π[sub u] states are also discussed.
ACCESSION #
9275717

 

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