A diabatic representation of the two lowest electronic states of Li{sub 3}

Journal Article · Mon Apr 21 04:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4871014· OSTI ID:22253111

Ghassemi, Elham Nour ^[1]; Larson, Jonas ^[2]; Larson, Åsa ^[2]

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1. Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands)
2. 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, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 140; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
CONFIGURATION INTERACTION
COUPLINGS
HAMILTONIANS
JAHN-TELLER EFFECT
POTENTIAL ENERGY
SURFACES