화학공학소재연구정보센터
Journal of Chemical Physics, Vol.105, No.4, 1500-1515, 1996
A Pseudopotential Hole-Particle Treatment of Neutral Rare-Gas Excimer Systems .2. The Rydberg States of the Ar-2-Asterisk Dimer
A pseudopotential hole-particle model (corresponding to the formalism introduced in paper I) is applied to the determination of the Rydberg states of the Ar-2* excimer with and without spin-orbit coupling. All the Lambda-Sigma Rydberg states (without spin-orbit coupling) adiabatically dissociating into Ar+Ar* (4s,4p,3d,5s,5p,4d), are investigated and all Omega states adiabatically dissociating into Ar+Ar*(4S,4p) have been determined including spin-orbit coupling. The calculation also includes at short distance attractive molecular configurations diabatically correlated with higher atomic asymptotes. The nature of the Lambda-Sigma states is analyzed acid assigned with reference to the Rydberg orbitals of the Kr* united atom limit. Extensive comparison with previous calculations and experiments is carried on. For the lowest ungerade states (1)1(u), O-u(+), (1)O-u(+), and (2)O-u(+), good quantitative agreement is found with experimental high resolution studies. Several members of Rydberg series are calculated and assigned, yielding intra-Rydberg transition energies (1)(3) Sigma(u)(+)((1)1(u),O-u(-))-->m (3) Pi(g) or m (3) Sigma(g)(+) in good correspondence with recent intra-Rydberg spectroscopy experiments, In particular the present calculation provides a likely interpretation of the infrared spectra of Ar-2* as due to (1)(3) Sigma(u)(+)-->(1)(3) Sigma(g)(+) transitions with an upper corresponding Omega state (1)1(g),O-g(-) containing quasi-bound vibrational levels.