Evolution of the electronic orbital alignment in metal-atom–rare-gas fractional collisions

We have developed an analytic model within the “orbital-locking and -following” approximation to explain the observed polarization spectrum in the metal-atom–rare-gas fractional collision experiments of Olsgaard and co-workers [Phys. Rev. A 48, 1987 (1993)]. We obtain an expression for the observed polarization spectrum that can be interpreted in terms of the evolution of the electronic orbital alignment from point to point on the intermediate excited-state potential-energy curve. The results, using model potentials for the metal-atom–rare-gas interaction, are in good agreement with the experimental polarization data.