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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 35, Number 5
BKCSDE 35(5)
May 20, 2014 

Study of the Valence and Rydberg States of a Lithium Dimer by the Multi-reference Configuration-interaction Method
Chun-Woo Lee
Lithium dimer, Excited rydberg states, Multi-reference CI
Convergent all-electron multi-reference configuration-interaction (MRCI) calculations are performed for a lithium dimer with Kaufmann's Rydberg basis functions. A comparison of the results of these calculations with those of the effective core potential/core polarization potential (ECP/CPP) method and experimental data reveals the deficiency of the all-electron ab initio method. The deficiency is related to the mere 51.9% attainment of electron correlation for the ground state. The percent attainment of electron correlation for the first excited state is slightly better than that for the ground state, preventing us from obtaining better agreements with experimental data by means of increasing the size of basis sets. The Kaufmann basis functions are then used with the ECP/CPP method to obtain the accurate convergent potential energy curves for the 1Πu states correlated to Li(2p) + Li(2p) and Li(2s) + Li(n = 2, 3, 4). Quantum defect curves (QDCs) calculated for both the X 2Σg and 1 2Πu states of the Li2 + ion and the Lu-Fano plot reveal a strong series-series interaction between the two 2snpπ and 2pnpπ Rydberg series. The QDCs are then used to resolve assignment problems in the literature. The reassignments, performed by Jedrzejewski-Szemek et al., of the dissociation product of the D 1Πu state from (2s+3d) to (2s+3p) and that of the 6 1Πu from (2s+4d) to (2s+4p) are found to be incorrect. It may be more natural to assign their 2snpπ Rydberg series as a 2sndπ series. The state, assigned as 5p 1Πu by Ross et al. and 4d 1Π by Jedrzejewski-Szemek et al., is assigned as the 7 1Πu state, correlated to the Li(2s) + Li(4f) limit.
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