On the size-consistency of the reduced-density-matrix method and the unitary invariant diagonal N-representability conditions
Source abstract
Abstract
A promising variational approach for determining the ground state energy and its properties is by using the second-order reduced density matrix (2-RDM). However, the leading obstacle with this approach is the N-representability problem. By employing a subset of conditions (typically the P, Q, G, T1 and T2′ conditions) results comparable to those of CCSD(T) can be achieved. However, these conditions do not guarantee size-consistency. In this work, we show that size-consistency can be satisfied if the 2-RDM satisfies the following conditions: (i) the 2-RDM is unitary invariant diagonal N-representable; (ii) the 2-RDM corresponding to each (unspecified) subsystem is the eigenstate of the number of corresponding electrons; and (iii) the 2-RDM satisfies at least one of the P, Q, G, T1 and T2′ conditions. This is the first time that a computationally feasible (though demanding) sufficient condition for the RDM method that guarantees size-consistency in all chemical systems has been published in the literature.
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Research context
OpenAlex topics: Advanced Chemical Physics Studies · Molecular Junctions and Nanostructures · Spectroscopy and Quantum Chemical Studies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Advanced Center for Computing and Communication 1 , RIKEN, 2-1 Hirosawa, Wako-city, Saitama, 351-0198, Japan
The University of Tokyo 2 Department of Physics, , 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan, 113-0033, Japan
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