Relativistic atomic natural orbital type basis sets for the alkaline and alkaline-earth atoms applied to the ground-state potentials for the corresponding dimers

被引:320
作者
Roos, BO [1 ]
Veryazov, V [1 ]
Widmark, PO [1 ]
机构
[1] Lund Univ, Ctr Chem, Dept Theoret Chem, S-22100 Lund, Sweden
关键词
relativistic basis sets; atomic natural orbitals; Douglas-Kroll; complete-active-space self-consistent field/complete-active-space second-order; perturbation theory;
D O I
10.1007/s00214-003-0537-0
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
New basis sets of the atomic natural orbital (ANO) type have been developed for the atoms Li-Fr and Be-Ra. The ANOs have been obtained from the average density matrix of the ground states and the lowest excited states of the atom, the positive ion, and the dimer at its equilibirium geometry. Scalar realtivisitc effects are included through the use of a Douglas-Kroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of the ground-state potentials for the dimers. Computed bond energies are accurate to within 0.05 eV for the alkaline dimers and 0.02 eV for the alkaline-earth dimers (except for Be-2).
引用
收藏
页码:345 / 351
页数:7
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