Two-electron reduced density matrices from the anti-Hermitian contracted Schrodinger equation: Enhanced energies and properties with larger basis sets

被引:64
作者
Mazziotti, David A. [1 ]
机构
[1] Univ Chicago, Dept Chem, Chicago, IL 60637 USA
[2] Univ Chicago, James Franck Inst, Chicago, IL 60637 USA
基金
美国国家科学基金会;
关键词
ELECTRONIC-STRUCTURE CALCULATIONS; DETERMINING QUANTUM ENERGIES; APPROXIMATE SOLUTION; CUMULANT EXPANSION; LOWER-ORDER; REPRESENTABILITY; SURFACES; TERMS; ATOMS;
D O I
10.1063/1.2723115
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
Two-electron reduced density matrices (2-RDMs) have recently been directly determined from the solution of the anti-Hermitian contracted Schrodinger equation (ACSE) to obtain 95%-100% of the ground-state correlation energy of atoms and molecules, which significantly improves upon the accuracy of the contracted Schrodinger equation (CSE) [D. A. Mazziotti, Phys. Rev. Lett. 97, 143002 (2006)]. Two subsets of the CSE, the ACSE and the contraction of the CSE onto the one-particle space, known as the 1,3-CSE, have two important properties: (i) dependence upon only the 3-RDM and (ii) inclusion of all second-order terms when the 3-RDM is reconstructed as only a first-order functional of the 2-RDM. The error in the 1,3-CSE has an important role as a stopping criterion in solving the ACSE for the 2-RDM. Using a computationally more efficient implementation of the ACSE, the author treats a variety of molecules, including H2O, NH3, HCN, and HO3-, in larger basis sets such as correlation-consistent polarized double- and triple-zeta. The ground-state energy of neon is also calculated in a polarized quadruple-zeta basis set with extrapolation to the complete basis-set limit, and the equilibrium bond length and harmonic frequency of N-2 are computed with comparison to experimental values. The author observes that increasing the basis set enhances the ability of the ACSE to capture correlation effects in ground-state energies and properties. In the triple-zeta basis set, for example, the ACSE yields energies and properties that are closer in accuracy to coupled cluster with single, double, and triple excitations than to coupled cluster with single and double excitations. In all basis sets, the computed 2-RDMs very closely satisfy known N-representability conditions. (c) 2007 American Institute of Physics.
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页数:9
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