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

Moriyama, H.; Wasada-Tsutsui, Y.; Sekiya, M.; Tatewaki, H.
March 2003
Journal of Chemical Physics;3/22/2003, Vol. 118 Issue 12, p5413
Academic Journal
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.


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