N -representability-driven reconstruction of the two-electron reduced-density matrix for a real-time time-dependent electronic structure method

• Published in: The Journal of chemical physics Vol. 141; no. 21; p. 214104
• Main Authors: Jeffcoat, David B., DePrince, A. Eugene
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 07.12.2014
• Subjects: COMPARATIVE EVALUATIONS; CONFIGURATION INTERACTION; Density; DENSITY MATRIX; DIPOLE MOMENTS; ELECTRIC FIELDS; ELECTRONIC STRUCTURE; ELECTRONS; EQUATIONS OF MOTION; EXCITATION; EXCITED STATES; Ground state; GROUND STATES; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; OPTIMIZATION; OSCILLATIONS; Physics; Symmetry; TIME DEPENDENCE; VARIATIONAL METHODS

Propagating the equations of motion (EOM) for the one-electron reduced-density matrix (1-RDM) requires knowledge of the corresponding two-electron RDM (2-RDM). We show that the indeterminacy of this expression can be removed through a constrained optimization that resembles the variational optimizat...