Electronic Structure of the Li2 [X (1)Sigma(+)(g)] + Li* [P-2] Excited (2)A '' Surface

摘要

Potential energy surface calculations are reported for the lowest (2)A '' surface arising from the Li-2 [X (1)Sigma(+)(g)] + Li* [P-2] interaction. The (2)A '' surface with C-s symmetry, which correlates to the (2)B1 surface in C-2v symmetry and to the (2)Pi surface in C-infinity v, has been calculated using second order restricted open-shell Moller-Plesset theory. Our calculated surface has a minimum in C-2v symmetry that resembles the ground state surface but does not exhibit the Jahn-Teller splitting found for the ground state potential energy surface. Dipole transition moments are calculated in C-2v geometry near the (2)A '' minima using the internally contracted multireference singles and doubles configuration interaction theory. We have also analyzed the long range behavior of this (2)A '' surface by fitting the ab initio calculations at long range with a functional series of the form +/- C-n/R-n.