Incremental embedding: A density matrix embedding scheme for molecules

Hong‐Zhou Ye

doi:10.1063/1.5053992

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Incremental embedding: A density matrix embedding scheme for molecules

2018-11-20

DOI：10.1063/1.5053992

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Abstract

En 中文

The idea of using fragment embedding to circumvent the high computational scaling of accurate electronic structure methods while retaining high accuracy has been a long-standing goal for quantum chemists. Traditional fragment embedding methods mainly focus on systems composed of weakly correlated parts and are insufficient when division across chemical bonds is unavoidable. Recently, density matrix embedding theory and other methods based on the Schmidt decomposition have emerged as a fresh approach to this problem. Despite their success on model systems, these methods can prove difficult for realistic systems because they rely on either a rigid, non-overlapping partition of the system or a specification of some special sites (i.e., edge and center sites), neither of which is well-defined in general for real molecules. In this work, we present a new Schmidt decomposition-based embedding scheme called incremental embedding that allows the combination of arbitrary overlapping fragments without the knowledge of edge sites. This method forms a convergent hierarchy in the sense that higher accuracy can be obtained by using fragments involving more sites. The computational scaling for the first few levels is lower than that of most correlated wave function methods. We present results for several small molecules in atom-centered Gaussian basis sets and demonstrate that incremental embedding converges quickly with fragment size and recovers most static correlation in small basis sets even when truncated at the second lowest level. Published by AIP Publishing.

Keywords:

EXCHANGE-CORRELATION POTENTIALS

ELECTRON CORRELATION

PERTURBATION-THEORY

LARGE SYSTEMS

FORMULATION

INVARIANT

ALGORITHM

ORBITALS

STATES

MODEL

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