A diabatic representation of the two lowest electronic states of Li{sub 3}
- Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands)
- Department of Physics, Stockholm University, AlbaNova University Center, SE-106 91 Stockholm (Sweden)
Using the Multi-Reference Configuration Interaction method, the adiabatic potential energy surfaces of Li{sub 3} are computed. The two lowest electronic states are bound and exhibit a conical intersection. By fitting the calculated potential energy surfaces to the cubic E ⊗ ε Jahn-Teller model we extract the effective Jahn-Teller parameters corresponding to Li{sub 3}. These are used to set up the transformation matrix which transforms from the adiabatic to a diabatic representation. This diabatization method gives a Hamiltonian for Li{sub 3} which is free from singular non-adiabatic couplings and should be accurate for large internuclear distances, and it thereby allows for bound dynamics in the vicinity of the conical intersection to be explored.
- OSTI ID:
- 22253111
- Journal Information:
- Journal of Chemical Physics, Vol. 140, Issue 15; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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