On the role of potential features in fine-structure transitions with application to H++F(2P½ →F(2P3/2)

Padmavathi, D. A. ; Rabitz, Herschel ; Mishra, Manoj K. (1994) On the role of potential features in fine-structure transitions with application to H++F(2P½ →F(2P3/2) Chemical Physics, 179 (3). pp. 469-478. ISSN 0301-0104

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/030101...

Related URL: http://dx.doi.org/10.1016/0301-0104(94)87023-3

Abstract

The first order functional sensitivity densities δln σ½ →3/2 (E)/dln W||Λ||(R) are employed to assess the role of structure in potential energy curves W0(R) and W1(R) involved in the fine-structure transition H++F(2P ½)→H++F(2P3/2 ). The results reveal that the fine-structure transition cross-section draws on the W0(2Σ) and W1(2Π) potentials in a highly correlated fashion and a measurement of σ½ →3/2 (E) for H++F will primarily allow information to be extracted only on the potential function difference W0(R)-W1(R) for moderate to large internuclear distances (R≥3 a0). While there is a marginal preference for the π alignment in the region where splitting between the 2Π and 2Σ curves is equal to the fine-structure transition energy, the oscillatory nature of the sensitivity densities with respect to R indicates that the alignment effects may disapper upon averaging over many impact parameters. The results from both functional sensitivity and adiabatic analysis isolate the region of potential energy curves centered at R≈7.8 a0 where the potential function difference W0(R)-W1(R) is equal to the fine-structure splitting, to be of maximum significance to the collisional fine-structure transition in this system.

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