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Density matrix variational theory: Application to the potential energy surfaces and strongly correlated systems

J. Chem. Phys. 116, 5432 (2002); doi:10.1063/1.1453961

Issue Date: 1 April 2002

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Maho Nakata, Masahiro Ehara, and Hiroshi Nakatsuji
Department of Synthetic Chemistry and Biological Chemistry, Faculty of Engineering, Kyoto University, Kyoto 606-8501, Japan
The density matrix variational theory (DMVT) algorithm developed previously [J. Chem. Phys. 114, 8282 (2001)] was utilized for calculations of the potential energy surfaces of molecules, H4, H2O, NH3, BH3, CO, N2, C2, and Be2. The DMVT(PQG), using the P, Q, and G conditions as subsidiary condition, reproduced the full-CI curves very accurately even up to the dissociation limit. The method described well the quasidegenerate states and the strongly correlated systems. On the other hand, the DMVT(PQ) was not satisfactory especially in the dissociation limit and its potential curves were always repulsive. The size consistency of the method was discussed and the G condition was found to be essential for the correct behavior of the potential curve. Further, we also examined the Weinhold–Wilson inequalities for the resultant 2-RDM of DMVT(PQG) calculations. Two linear inequalities were violated when the results were less accurate, suggesting that this inequality may provide a useful N-representability condition for the DMVT. ©2002 American Institute of Physics.
History: Received 23 August 2001; accepted 7 January 2002
Permalink: http://link.aip.org/link/?JCPSA6/116/5432/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.50.-x
    Electronic structure of atoms and molecules: theory Potential energy surfaces
  • 31.15.Pf
    Electronic structure of atoms and molecules: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Variational techniques
  • 31.25.Nj
    Electronic structure of atoms and molecules: theory Electron correlation calculations for atoms and molecules Electron correlation calculations for diatomic molecules
  • 31.25.Qm
    Electronic structure of atoms and molecules: theory Electron correlation calculations for atoms and molecules Electron correlation calculations for polyatomic molecules
  • 02.30.Xx
    Mathematical methods in physics Function theory, analysis Calculus of variations
  • YEAR: 2002

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0021-9606 (print)   1089-7690 (online)
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