Electronic structure of the Li2 [X 1 Σ] Li [ 2 p] excited 2 A″ surface

• Published in: International journal of quantum chemistry Vol. 109; no. 15; pp. 3626 - 3631
• Main Authors: Byrd, Jason N., Montgomery, John A., Michels, H. Harvey, Côté, Robin
• Format: Journal Article
• Language: English
• Published: 01.12.2009
• ISSN: 0020-7608; 1097-461X
• DOI: 10.1002/qua.22414

Abstract Potential energy surface calculations are reported for the lowest 2 A″ surface arising from the Li 2 [X 1 Σ ] + Li* [ 2 P] 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 ∞v , has been calculated using second order restricted open‐shell Møller–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 . © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009