2021-11-29T12:48:41Zhttps://nagoya.repo.nii.ac.jp/oaioai:nagoya.repo.nii.ac.jp:000070672021-03-01T12:28:40ZDirect determination of the quantum-mechanical density matrix: Parquet theoryYasuda, KojiCopyright: American Physical Society, All rights reserved.The methods used to determine the reduced density matrix (RDM) of the ground and excited states, the finite-temperature systems, and the large systems without using the wave function by solving the density equation were discussed. We examined the foundations to reconstruct the higher-order RDMs of the ground and excited states and the finite-temperature systems in terms of the lower-order RDMs. We presented the equation to determine the RDMs of the finite-temperature systems directly and showed that only the exact RDMs satisfy the equation. Our previous approximation for third- and fourth-order RDMs of the ground state [H. Nakatsuji and K. Yasuda, Phys. Rev. Lett. 76, 1039 (1996)] was reformulated, and the accuracy of this approximation for the excited states was examined. The structure of the nth order energy density matrix (n-EDM) was analyzed, and the calculation method which sums up the Parquet diagram of the 2-EDM without explicitly constructing the third- and fourth-order RDMs was reported. This approximation is more accurate than the previous second-order approximation and also includes the infinite series of bubble and ladder Greenâ€™s function diagrams. Such a method is necessary to apply the density-equation method to large systems, such as polymers, metals, and semiconductors. The new approximation together with the density equation was applied to the ground states of some molecules including CO, C2H2, C3H8, and C4H10 , and the excited states of the Be atom and Li2 molecule. The calculated energies were as accurate as the exact or coupled-cluster single and double excitations with triples included noniteratively, and the energy errors of the second-order approximation were significantly reduced. The calculated 2-RDMs almost satisfied important representability conditions while the 1-RDMs were exactly ensemble representable. These results demonstrate that the density equation offers a new quantitative method for treating electron correlations. The relationship between the iterative procedure and the finite-temperature density-equation method was discussed.American Physical Society1999-06engjournal articlehttp://hdl.handle.net/2237/8741https://nagoya.repo.nii.ac.jp/records/7067http://dx.doi.org/10.1103/PhysRevA.59.4133PHYSICAL REVIEW A59641334149https://nagoya.repo.nii.ac.jp/record/7067/files/PhysRevA59-4133.pdfapplication/pdf289.4 kB2018-02-19