Enhanced computational efficiency in the direct determination of the two-electron reduced density matrix from the anti-Hermitian contracted Schrödinger equation with application to ground and excited states of conjugated π-systems.

Abstract

Determination of the two-electron reduced density matrix (2-RDM) from the solution of the anti-Hermitian contracted Schrödinger equation (ACSE) yields accurate energies and properties for both ground and excited states. Here, we develop a more efficient method to solving the ACSE that uses second-order information to select a more optimal step towards the solution. Calculations on the ground and excited states of water, hydrogen fluoride, and conjugated π systems show that the improved ACSE algorithm is 10-20 times faster than the previous ACSE algorithm. The ACSE can treat both single- and multi-reference electron correlation with the initial 2-RDM from a complete-active-space self-consistent-field (CASSCF) calculation. Using the improved algorithm, we explore the relationship between truncation of the active space in the CASSCF calculation and the accuracy of the energy and 2-RDM from the ACSE calculation. The accuracy of the ACSE, we find, is less sensitive to the size of the active space than the accuracy of other wavefunction methods, which is useful when large active space calculations are computationally infeasible.