A benchmark study of Li-2(+) Li-2(-), LiH+ and LiH-: Quantum Monte-Carlo and coupled-cluster computations

作者：Nasiri Saeed; Zahedi Mansour^*

来源：Computational and Theoretical Chemistry, 2017, 1114: 106-117.

DOI：10.1016/j.comptc.2017.05.015

• Lithium dimer ions
• Lithium hydride ions
• Potential energy curve
• Quantum Monte-Carlo method
• Coupled-cluster method
• Correlation energy

For the first time, very accurate potential energy curves (PEC) have been computed by the all electron Diffusion Quantum Monte-Carlo (DMC) and CCSD(T) methods for the ground-state of the Li-2(+), Li-2(-), LiH+ and LiH- ions. In addition to the molecular moieties, Li+, Li-, H- ions have also been studied by the aforementioned methods. The employed trial wave functions for the DMC calculations are a multiplication of multi-configuration expansions which are prepared by the Complete Active Space Self-Consistent Field method (CASSCF) with the aug-cc-pVTZ and the aug-cc-pCVTZ basis sets and the Jastrow factor. The CCSD(T) computations with all electrons correlated, have been performed by the cc-pV5Z, aug-cc-pCVQZ and aug-cc-pV6Z basis sets. In addition, the correlation energies for all of the studied atomic and molecular species have been calculated. For the studied molecular species, the Hartree-Fock energies in the complete basis set limit (E-CBS) have not been reported. In this work for each of the molecular systems, the most negative energy which has been computed by the cc-pV5Z or aug-cc-pCVQZ basis sets has been used. The obtained PECs by the DMC and CCSD(T) methods are used to calculate the vibration rotation energy levels and spectroscopic constants.

• 出版日期2017-8-15