Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Variational reduced-density-matrix method using three-particle N -representability conditions with application to many-electron molecules

Variational reduced-density-matrix method using three-particle N -representability conditions... Molecular two-electron reduced density matrices (2-RDMs) are computed variationally without the many-electron wave function by constraining the 2-RDM with a set of three-particle N -representability conditions known as three-positivity conditions. These constraints restrict four distinct three-particle probability distributions, which can be defined for any N -particle system, to be nonnegative. The variational calculation of the 2-RDM with full three-positivity conditions is implemented with the first-order semidefinite programming algorithm D.A. Mazziotti , Phys. Rev. Lett. 93 , 213001 ( 2004 ) . We also derive and implement a generalization of the T 2 representability condition, which is a subset of the three-positivity conditions. Energies and 2-RDMs are computed for several molecules as well as the nitrogen molecule at both equilibrium and nonequilibrium geometries. The ground-state energies for nitrogen are within 0.0015 a.u. of the values from full configuration interaction at all internuclear distances. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Physical Review A American Physical Society (APS)

Variational reduced-density-matrix method using three-particle N -representability conditions with application to many-electron molecules

Physical Review A , Volume 74 (3) – Sep 1, 2006
9 pages

Loading next page...
 
/lp/american-physical-society-aps/variational-reduced-density-matrix-method-using-three-particle-n-0RIuzj2E0j

References

References for this paper are not available at this time. We will be adding them shortly, thank you for your patience.

Publisher
American Physical Society (APS)
Copyright
Copyright © 2006 The American Physical Society
ISSN
1094-1622
DOI
10.1103/PhysRevA.74.032501
Publisher site
See Article on Publisher Site

Abstract

Molecular two-electron reduced density matrices (2-RDMs) are computed variationally without the many-electron wave function by constraining the 2-RDM with a set of three-particle N -representability conditions known as three-positivity conditions. These constraints restrict four distinct three-particle probability distributions, which can be defined for any N -particle system, to be nonnegative. The variational calculation of the 2-RDM with full three-positivity conditions is implemented with the first-order semidefinite programming algorithm D.A. Mazziotti , Phys. Rev. Lett. 93 , 213001 ( 2004 ) . We also derive and implement a generalization of the T 2 representability condition, which is a subset of the three-positivity conditions. Energies and 2-RDMs are computed for several molecules as well as the nitrogen molecule at both equilibrium and nonequilibrium geometries. The ground-state energies for nitrogen are within 0.0015 a.u. of the values from full configuration interaction at all internuclear distances.

Journal

Physical Review AAmerican Physical Society (APS)

Published: Sep 1, 2006

There are no references for this article.