Molecular properties from variational reduced-density-matrix theory with three-particle N-representability conditions |
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Authors: | Gidofalvi Gergely Mazziotti David A |
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Institution: | Department of Chemistry, The James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA. |
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Abstract: | Molecular ground-state energies and two-electron reduced density matrices (2-RDMs) have recently been computed without the many-electron wave function by constraining the 2-RDM to satisfy a complete set of three-positivity conditions for N representability D. A. Mazziotti, Phys. Rev. A 74, 032501 (2006)]. Energies at both equilibrium and nonequilibrium geometries are obtained within 0.3% of the correlation energy. In this paper the authors extend this work to examine the accuracy of molecular properties, including multipole moments and components of the ground-state energy, relative to full configuration interaction (FCI). Comparisons are also made with 2-RDM methods with two-positivity conditions and two-positivity plus the generalized T1T2 conditions as well as several approximate wave function methods. Using the 2-RDM method with three-positivity conditions, the authors obtain dipole, quadrupole, and octupole moments for BeH2, BH, H2O, CO, and NH3 at equilibrium geometries that are within 0.04% of their FCI values. In addition, for the potential energy surface of N2, the 2-RDM method with three-positivity yields not only accurate total ground-state energies but also accurate expectation values of the kinetic energy operator, the electron-nuclei potential, and electron-electron repulsion. |
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