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Ab Initio Diabatic energies and dipole moments of the electronic states of RbLi molecule
Author(s) -
Dardouri Riadh,
Habli Héla,
Oujia Brahim,
Gadéa Florent Xavier
Publication year - 2013
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23363
Subject(s) - diabatic , pseudopotential , ab initio , dipole , chemistry , atomic physics , excited state , configuration interaction , valence (chemistry) , ab initio quantum chemistry methods , electronic structure , adiabatic process , diatomic molecule , physics , molecule , computational chemistry , quantum mechanics , organic chemistry
For all states dissociating below the ionic limit Li − Rb + , we perform a diabatic study for 1 Σ + electronic states dissociating into Rb (5s, 5p, 4d, 6s, 6p, 5d, 7s, 4f) + Li (2s, 2p, 3s). Furthermore, we present the diabatic results for the 1–11 3 σ, 1–8 1,3 Π, and 1–4 1,3 Δ states. The present calculations on the RbLi molecule are complementary to previous theoretical work on this system, including recently observed electronic states that had not been calculated previously. The calculations rely on ab‐initio pseudopotential, core polarization potential operators for the core‐valence correlation and full valence configuration interaction approaches, combined to an efficient diabatization procedure. For the low‐lying states, diabatic potentials and permanent dipole moments are analyzed, revealing the strong imprint of the ionic state in the 1 Σ + adiabatic states. The transition dipole moment is used to evaluate the radiative lifetimes of the vibrational levels trapped in the 2 1 Σ + excited states for the first time. In addition to the bound–bound contribution, the bound–free term has been evaluated using the Franck–Condon approximation and also exactly added to the total radiative lifetime. © 2013 Wiley Periodicals, Inc.