Pair 2-electron reduced density matrix theory using localized orbitals

被引:29
|
作者
Head-Marsden, Kade
Mazziotti, David A. [1 ]
机构
[1] Univ Chicago, Dept Chem, 5735 S Ellis Ave, Chicago, IL 60637 USA
来源
JOURNAL OF CHEMICAL PHYSICS | 2017年 / 147卷 / 08期
基金
美国国家科学基金会;
关键词
GENERALIZED ANTISYMMETRIZED PRODUCT; NATURAL SPIN-ORBITALS; WAVE-FUNCTIONS; REPRESENTABILITY PROBLEM; COUPLED-CLUSTER; BASIS-SETS; CONFIGURATIONAL INTERACTION; NONORTHOGONAL GEMINALS; MOLECULAR-ORBITALS; ATOMS;
D O I
10.1063/1.4999423
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
Full configuration interaction (FCI) restricted to a pairing space yields size-extensive correlation energies but its cost scales exponentially with molecular size. Restricting the variational two-electron reduced-density-matrix (2-RDM) method to represent the same pairing space yields an accurate lower bound to the pair FCI energy at a mean-field-like computational scaling of O (r(3)) where r is the number of orbitals. In this paper, we show that localized molecular orbitals can be employed to generate an efficient, approximately size-extensive pair 2-RDM method. The use of localized orbitals eliminates the substantial cost of optimizing iteratively the orbitals defining the pairing space without compromising accuracy. In contrast to the localized orbitals, the use of canonical Hartree-Fock molecular orbitals is shown to be both inaccurate and non-size-extensive. The pair 2-RDM has the flexibility to describe the spectra of one-electron RDM occupation numbers from all quantum states that are invariant to time-reversal symmetry. Applications are made to hydrogen chains and their dissociation, n-acene from naphthalene through octacene, and cadmium telluride 2-, 3-, and 4-unit polymers. For the hydrogen chains, the pair 2-RDM method recovers the majority of the energy obtained from similar calculations that iteratively optimize the orbitals. The localized-orbital pair 2-RDM method with its mean-field-like computational scaling and its ability to describe multireference correlation has important applications to a range of strongly correlated phenomena in chemistry and physics. Published by AIP Publishing.
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页数:7
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